JP2019038880A - Resin composition for laser welding and welded body of the same - Google Patents

Abstract

To provide a polyester resin composition for laser welding from which a laser-welded welded body has high flame retardancy, has a high weld strength, is excellent in thermal discoloration resistance, exhibits black coloring excellent in coloring power, and has further excellent laser welding workability.SOLUTION: A resin composition is used for welding with a laser beam contains 0.0005-0.5 pts.mass of (B) nigrosine, 0.01-2 pts.mass of (C) a coloring agent containing an anthraquinone dye and 2.5-100 pts.mass of (D) a bromine-based flame retardant, with respect to 100 pts.mass of (A) a thermoplastic polyester resin material containing polybutylene terephthalate homopolymer and/or polybutylene terephthalate copolymer.SELECTED DRAWING: Figure 4

Description

  The present invention relates to a laser-welded resin composition and a welded body, and a welded body obtained by laser welding a molded product obtained from a laser-welded resin composition has high flame retardancy and high weld strength. Furthermore, it is a polyester resin composition for laser welding that is also excellent in laser welding processability.

Thermoplastic polyester resin has excellent mechanical strength, chemical resistance, electrical insulation, etc., and has excellent heat resistance, moldability, and recyclability, so it is widely used in various equipment parts. It has been.
In recent years, parts for automobiles have been reduced in weight in particular, and a high level of heat resistance is often demanded due to resin conversion of parts that have conventionally used metals, miniaturization of resin products, and the like. For this reason, reinforced thermoplastic resins containing fillers such as glass fibers are often used, among which thermoplastic polyester resins such as polybutylene terephthalate are excellent in mechanical strength and moldability and can be made flame retardant by adding flame retardants. Since it is possible, it is widely used for automobile electronic component cases, motor component cases, and the like.

In recent years, an example of performing welding processing for increasing productivity has been increasing, and laser welding, which has little influence on electronic components, has been frequently used.
However, compared to polycarbonate resins, polystyrene resins, and the like, polyester resins have relatively low laser light transmittance, and warping tends to occur in molded products, so that the welding strength is often insufficient. In particular, when the polyester resin is made flame retardant, the laser beam permeability is remarkably lowered and the welding strength is insufficient.
When warping occurs in the molded product, a method of applying a pressing force to correct the warping at the time of welding is also taken, but depending on the shape of the molded product, it is often difficult to apply the pressing force efficiently. Since residual stress remains in the welded body from which the pressing force has been removed later, there is a problem that high weld strength is difficult to obtain.

In order to improve the laser weldability of the polyester resin, a method using a copolymerized polybutylene terephthalate (Patent Document 1), a method of alloying a polybutylene terephthalate with a polycarbonate resin or a styrene resin (Patent Documents 2 and 3), Furthermore, a method of adding a specific oligomer (Patent Document 4) has been proposed.
However, in these methods, sufficient weldability may not be obtained due to a gap between welding members caused by warpage deformation of a molded product.
In addition, a method for improving weldability by adding a laser transmission absorbent such as nigrosine to a thermoplastic resin has been proposed (Patent Document 5), but a polyester resin composition suitable for laser welding has not been described. Absent.

Japanese Patent No. 3510817 Japanese Patent Laid-Open No. 2003-292752 Japanese Patent No. 4641377 JP 2004-315805 A JP 2008-1112 A

  An object of the present invention is to provide a laser-welded polyester resin composition having excellent welding processability by laser, excellent black coloring power and flame retardancy, and excellent welding strength of a welded body obtained by laser welding. It is in.

The present inventors use the brominated flame retardant, nigrosine, and a specific colorant in combination with a thermoplastic polyester resin material containing a polybutylene terephthalate homopolymer and / or a polybutylene terephthalate copolymer. The inventors have found that this can be solved and have reached the present invention.
The present invention relates to the following laser-welded resin composition, laser-welded molded body, and laser-welded body.

[1] A resin composition used for laser beam welding,
(A) For 100 parts by mass of a thermoplastic polyester resin material containing a polybutylene terephthalate homopolymer and / or a polybutylene terephthalate copolymer,
(B) Nigrosine 0.0005 to 0.5 parts by mass,
(C) 0.01-2 parts by weight of a colorant containing an anthraquinone dye, and
(D) A laser welding resin composition comprising 2.5 to 100 parts by mass of a brominated flame retardant.

[2] (C) The colorant contains perinone dye C2 having a maximum absorption wavelength in the range of 460 to 480 nm and anthraquinone dye C1 in which the maximum absorption wavelength is in the range of 590 to 635 nm, and the mass ratio C2 / C1 between the two is 0. The resin composition for laser welding according to the above [1], which is a colorant contained in a ratio of 4 to 2.
[3] (A) The thermoplastic polyester-based resin material includes a polybutylene terephthalate homopolymer and a polybutylene terephthalate copolymer, and the content of the polybutylene terephthalate copolymer is 5 to 95 mass with respect to the total of 100 mass% of both. % [1] or [2], the laser welding resin composition.
[4] (A) The thermoplastic polyester-based resin material includes a polybutylene terephthalate homopolymer and a polyethylene terephthalate resin, and the content of the polyethylene terephthalate resin is 5 to 50% by mass with respect to the total of 100% by mass of both. The laser welding resin composition according to any one of the above [1] to [3].
[5] (A) The thermoplastic polyester resin material includes a polybutylene terephthalate homopolymer and a polycarbonate resin, and the content of the polycarbonate resin is 5 with respect to a total of 100% by mass of the polybutylene terephthalate homopolymer and the polycarbonate resin. Laser welding resin composition as described in said [1] or [2] which is -50 mass%.
[6] The laser welding resin composition according to any one of [1] to [5], wherein (D) the brominated flame retardant is brominated acrylate.

[7] Absorbance a _0.75 (absorbance converted to a molded plate having a thickness of 0.75 mm) with respect to a laser beam of 940 nm of the molded plate made of the resin composition is 0.05 to _1.5. ] The resin composition for laser welding as described in any one of [6].
[8] The incident rate K _0.75 (incidence rate converted to a molded plate having a thickness of 0.75 mm) with respect to a laser beam of 940 nm of the molded plate made of the resin composition is 15 to 80% [1] The resin composition for laser welding according to any one of to [7].
However, the incidence rate K _0.75 is calculated as follows using the transmittance T _0.75 and the reflectance R _0.75 at a thickness of _0.75 mm.
Incidence factor K _0.75 (%) = 100−T _0.75 −R _0.75

[9] A molded article for laser welding comprising the resin composition for laser welding according to any one of [1] to [8].
[10] A laser welded body of the molded product according to [9].
[11] The laser welded body according to the above [10], wherein the welded body has a gap of 0.1 mm or more when the welded body is welded at least in a part of the welded portion.
[12] The laser welded body according to the above [10] or [11], wherein the compacts are butted and welded together.
[13] The laser welded body according to [10] or [11], in which the compacts are overlapped and welded.

  The resin composition for laser welding of the present invention has excellent black coloring power and flame retardancy, has suitable laser welding processability, and a welded body obtained by laser welding a molded body of the resin composition has a welding strength and a black coloring. Excellent.

FIG. 1 is an ultraviolet-visible spectroscopic spectrum diagram of each dye used in Production Example 1 of a colorant. FIG. 2 is a diagram showing an example of manufacturing a laser welded body by abutting a plurality of molded bodies and performing laser welding. FIG. 3 is a diagram showing an example of manufacturing a laser welded body by laminating a plurality of molded bodies and performing laser welding. FIG. 4 is a conceptual diagram showing a method of superposition laser welding in the embodiment.

  Hereinafter, although the form for implementing this invention is demonstrated in detail, the scope of the present invention is not limited to these forms. In the specification of the present application, “to” is used in the sense of including the numerical values described before and after it as lower and upper limits.

Laser welding resin composition of the present invention,
A resin composition used for welding by laser light,
(A) For 100 parts by mass of a thermoplastic polyester resin material containing a polybutylene terephthalate homopolymer and / or a polybutylene terephthalate copolymer,
(B) Nigrosine 0.0005 to 0.5 parts by mass,
(C) 0.01-2 parts by weight of a colorant containing an anthraquinone dye, and
(D) It contains 2.5 to 100 parts by mass of a brominated flame retardant.

[(B) Nigrosine]
The resin composition for laser welding of the present invention contains (B) nigrosine.
Nigrosine works as a dye having laser light absorption, and has gentle absorption in the range of 800 nm to 1200 nm laser light.
Nigrosine is C.I. I. Solvent Black 5 and C.I. I. It is a black azine-based condensation mixture as described in Color Index as Solvent Black 7. This can be synthesized, for example, by oxidizing and dehydrating condensation of aniline, aniline hydrochloride and nitrobenzene at a reaction temperature of 160 to 190 ° C. in the presence of iron chloride. Examples of commercially available nigrosine include “NUBIAN (registered trademark) BLACK series” (trade name, manufactured by Orient Chemical Industry Co., Ltd.).

The content of (B) nigrosine is 0.0005 to 0.5 parts by mass with respect to 100 parts by mass of the (A) thermoplastic polyester resin material. It is -0.1 mass part, More preferably, it is 0.003-0.05 mass part, More preferably, it is 0.005-0.03 mass part.
In addition, when the above-mentioned content (A) thermoplastic polyester-based resin material contains a resin other than a thermoplastic polyester-based resin, a polycarbonate resin, etc. It is the quantity with respect to 100 mass parts in total.

By adjusting the content of nigrosine in such a range, it becomes possible to balance the transmittance and reflectance of the molded body. In the present invention, this is defined as the incidence rate.
The incidence rate K _0.75 (incidence rate converted to a molded plate having a thickness of 0.75 mm) of the laser welding resin composition is preferably 15 to 80%, more preferably 25 to 75%, and particularly preferably 30 to 70. %. In addition, by adding nigrosine, it is possible to improve the black coloring power, improve the surface appearance and smoothness of the molded article, and improve the laser weldability.
Incidentally, incidence rate _{K 0.75} (unit:%) in the thickness 0.75mm is defined by the following equation using the transmittance _{T 0.75} and _{R 0.75} of 0.75mm thickness.
Incidence factor K _0.75 (%) = 100−T _0.75 −R _0.75
Incident rate _K0.75 is an incident rate with respect to the laser beam of wavelength 940nm when a molded object is 0.75mm thick.
In the case of a molded body of 60 mm long x 60 mm wide x 0.75 mm thick, it is derived from the measurement results of transmittance and reflectance of the part on the side opposite to the gate (the part on the opposite side of the gate into which the resin is injected). . The molded body is manufactured under conditions of a cylinder temperature of 255 ° C., a mold temperature of 80 ° C., and an injection speed of 75 mm / sec.
Moreover, the resin composition for laser welding may contain the other absorptive dye with respect to a laser beam, or a laser beam absorber in the effective range which can implement this invention.

[(C) Colorant]
As the colorant (C) used in the laser welding resin composition of the present invention, a colorant containing an anthraquinone dye is used.
Further, (C) the colorant contains a perinone dye C2 having a maximum absorption wavelength in the range of 460 to 480 nm and an anthraquinone dye C1 having a maximum absorption wavelength in the range of 590 to 635 nm, and the mass ratio C2 / C1 of the two is 0. It is preferable that the colorant is contained at a ratio of 4 to 2.
More preferably, the anthraquinone dye C1 whose maximum absorption wavelength is in the range of 590 to 635 nm, the perinone dye C2 whose maximum absorption wavelength is in the range of 460 to 480 nm, and the anthraquinone dye C3 whose maximum absorption wavelength is in the range of 435 to 455 nm May be used in combination. What is contained at least by C1: C2: C3 = 24-42: 24-48: 22-46 by the mass ratio with respect to a total of 100 mass parts of the anthraquinone dye C1, the perinone dye C2, and the anthraquinone dye C3 which are the said dye is preferable.
In addition, the maximum absorption wavelength is defined as a wavelength exhibiting maximum absorption in an absorption spectrum obtained by measuring a solution dissolved in dimethylformamide (DMF) using an ultraviolet-visible spectrophotometer.

The colorant of the present invention will be described in detail.
(C) The colorant has absorption in the visible region, (A) has good compatibility with the thermoplastic polyester resin material, and requires a combination of dyes with less scattering characteristics with respect to laser light. Even when exposed to high temperatures during melting or melting, it is desirable that the material does not easily fade and has excellent heat resistance.
The anthraquinone dye C1 having a maximum absorption wavelength in the range of 590 to 635 nm, which is preferably used as the (C) colorant of the present invention, is usually a blue oil-soluble dye. In the present invention, by using this dye, for example, the visibility is higher than that of a green anthraquinone dye, and even when a black mixed dye is combined, a subtractive color mixture can be used to combine a red dye and a yellow dye to increase coloring power. A colorant exhibiting black color can be obtained.

As the anthraquinone dye C1 having a maximum absorption wavelength in the range of 590 to 635 nm, it is preferable to select one having a thermogravimetric analyzer TG / DTA measurement value (decomposition start temperature) of 300 ° C. or higher in the presence of air.
A preferred anthraquinone dye C1 is C.I. as described in COLOR INDEX. I. Solvent Blue 97 (decomposition start temperature 320 ° C.), C.I. I. Solvent blue 104 (decomposition start temperature 320 degreeC) etc. are illustrated. One or more of them may be used. However, when the blending amount is increased, the molded product tends to bleed in a high temperature atmosphere, and the heat discoloration property tends to deteriorate.
Examples of the commercially available anthraquinone dye C1 include “NUBIAN (registered trademark) BLUE series” and “OPLAS (registered trademark) BLUE series” (both trade names, manufactured by Orient Chemical Industry Co., Ltd.).

In the present invention, as the colorant (C), a perinone dye C2 having a maximum absorption wavelength in the range of 460 to 480 nm is preferably used in combination with the above-described anthraquinone dye C1. These are usually red oil-soluble dyes. Specific examples of such perinone dye C2 include C.I. I. Solvent Red 135, 162, 178, 179 etc. can be used. One or more of them may be used. However, when the blending amount is increased, the molded product tends to bleed in a high temperature atmosphere, and the heat discoloration property tends to deteriorate.
Examples of the commercially available red perinone dye C2 include “NUBIAN (registered trademark) RED series, OPLAS (registered trademark) RED series” (both manufactured by Orient Chemical Industry Co., Ltd.) and the like.

In the present invention, in addition to the above-mentioned dyes C1 and C2, it is also preferable to use a combination of an anthraquinone dye C3 having good heat resistance with a maximum absorption wavelength in the range of 435 to 455 nm. Anthraquinone dye C3 having a maximum absorption wavelength in the range of 435 to 455 nm is usually a yellow oil-soluble dye.
Specific examples of the anthraquinone dye C3 having a maximum absorption wavelength in the range of 435 to 455 nm include C.I. I. Solvent Yellow 163, C.I. I. Vat Yellow 1, 2, 3, etc. can be used. One or more of them may be used. However, when the blending amount is increased, the molded product tends to bleed in a high temperature atmosphere, and the heat discoloration property tends to deteriorate.
Examples of commercially available yellow anthraquinone dyes as such anthraquinone dye C3 include “NUBIAN (registered trademark) YELLOW series, OPLAS (registered trademark) YELLOW series” (both trade names, manufactured by Orient Chemical Industries). Can be mentioned.

  The colorant (C) used in the present invention has an anthraquinone dye C1 having a maximum absorption wavelength in the range of 590 to 635 nm, a perinone dye C2 in which the maximum absorption wavelength is in the range of 460 to 480 nm, and a maximum absorption wavelength of 435 to 455 nm. It is preferable to use an anthraquinone dye C3 in the range of the above, but the hue of the oil-soluble dye constituting (B) nigrosine and (C) the colorant changes depending on the compatibility with the polybutylene terephthalate homopolymer. It is necessary to adjust the ratio of the oil-soluble dye constituting the colorant (C) in order to obtain a suitable jet black molded plate. Therefore, the content ratio of C1 to C3 is preferably C1: C2: C3 = 24 to 42:24 to 48:22 to 46 in terms of mass ratio (based on a total of 100 parts by mass of C1, C2, and C3). A more preferable ratio of C1: C2: C3 is 24-41: 24-39: 22-46.

  Furthermore, in the present invention, (C) the colorant comprises a perinone dye C2 having a maximum absorption wavelength in the range of 460 to 480 nm and an anthraquinone dye C1 having a maximum absorption wavelength in the range of 590 to 635 nm, and a mass ratio C2 / C1 between them. Is preferably a colorant contained in a ratio of 0.4 to 2. In consideration of color developability and bleed-out suppression by the resin composition of the present invention, it is more preferably 0.4 to 1.5, still more preferably 0.61 to 1.5.

  (C) Content of a coloring agent is 0.01-2 mass parts with respect to 100 mass parts of (A) thermoplastic polyester-type resin materials, Preferably it is 0.05-0.8 mass part, More preferably, it is. 0.1 to 0.6 parts by mass. By adjusting the content of the colorant to such a range, a laser welding resin composition having a high black coloring power can be obtained.

In the present invention, the (C) colorant may contain a dye other than C1, C2 and C3 described above, but preferably does not contain a nickel complex.
Other dyes that may be used in combination include azo dyes, quinacridone dyes, dioxazine dyes, quinophthalone dyes, perylene dyes, perinone dyes (compounds having a wavelength different from C2 described above), isoindolinone dyes, triphenylmethane dyes, anthraquinones And dyes such as dyes (compounds having wavelengths different from those of C1 and C3 described above).

[(A) Thermoplastic polyester resin material]
The thermoplastic polyester resin material (A) contained in the laser welding resin composition of the present invention contains a polybutylene terephthalate homopolymer (A1a) and / or a polybutylene terephthalate copolymer (A1b). A2a) or polyethylene terephthalate resin (A2b) may further be included.

<Polybutylene terephthalate homopolymer (A1a)>
The polybutylene terephthalate homopolymer (A1a) used in the thermoplastic polyester resin material (A) of the present invention is a polymer obtained by polycondensation of terephthalic acid as an acid component and 1,4-butanediol as an alcohol component. It is.

The intrinsic viscosity of the polybutylene terephthalate homopolymer (A1a) is preferably 0.5 to 2 dl / g. From the viewpoint of moldability and mechanical properties, those having an intrinsic viscosity in the range of 0.6 to 1.5 dl / g are more preferable. If a material having an intrinsic viscosity lower than 0.5 dl / g is used, the obtained welding member tends to have a low mechanical strength. Moreover, in the thing higher than 2 dl / g, the fluidity | liquidity of (A) thermoplastic polyester-type resin material worsens, a moldability may deteriorate, or laser weldability may fall.
The intrinsic viscosity is a value measured at 30 ° C. in a 1: 1 (mass ratio) mixed solvent of tetrachloroethane and phenol.

  The terminal carboxyl group amount of the polybutylene terephthalate homopolymer (A1a) may be appropriately selected and determined, but is usually 60 eq / ton or less, preferably 50 eq / ton or less, and preferably 30 eq / ton or less. More preferably. If it exceeds 50 eq / ton, gas tends to be generated during the melt molding of the (A) thermoplastic polyester resin material. The lower limit value of the terminal carboxyl group amount is not particularly defined, but is usually 5 eq / ton.

  The amount of terminal carboxyl groups of polybutylene terephthalate homopolymer (A1a) is obtained by dissolving 0.5 g of resin in 25 mL of benzyl alcohol and titrating with 0.01 mol / l benzyl alcohol solution of sodium hydroxide. This is the required value. As a method for adjusting the amount of terminal carboxyl groups, a conventionally known arbitrary method such as a method for adjusting polymerization conditions such as a raw material charge ratio during polymerization, a polymerization temperature, a pressure reduction method, a method for reacting a terminal blocking agent, etc. Just do it.

<Polybutylene terephthalate copolymer (A1b)>
(A) The polybutylene terephthalate copolymer (A1b) used for the thermoplastic polyester resin material is preferably isophthalic acid, dimer acid, polytetramethylene glycol (PTMG) in addition to terephthalic acid and 1,4-butanediol. It is a polymer obtained by copolymerizing a polyalkylene glycol or the like.

  When using a copolymer of polytetramethylene glycol as the polybutylene terephthalate copolymer (A1b), the proportion of the tetramethylene glycol component in the copolymer is preferably 3 to 40% by mass, and 5 to 30% by mass. % Is more preferable, and 10 to 25% by mass is still more preferable. By setting it as such a copolymerization ratio, it tends to be excellent in the balance between laser weldability and heat resistance, which is preferable.

  When dimer acid copolymerized polybutylene terephthalate is used as the polybutylene terephthalate copolymer (A1b), the proportion of the dimer acid component in the total carboxylic acid component is preferably 0.5 to 30 mol% as the carboxylic acid group. 1-20 mol% is more preferable, and 3-15 mol% is still more preferable. By setting it as such a copolymerization ratio, it exists in the tendency which is excellent in the balance of laser weldability, long-term heat resistance, and toughness, and is preferable.

  When isophthalic acid copolymerized polybutylene terephthalate is used as the polybutylene terephthalate copolymer (A1b), the proportion of the isophthalic acid component in the total carboxylic acid component is preferably 1 to 30 mol% as the carboxylic acid group. -20 mol% is more preferable, and 3-15 mol% is still more preferable. By setting it as such a copolymerization ratio, it exists in the tendency which is excellent in the balance of laser weldability, heat resistance, injection moldability, and toughness, and is preferable.

  Among these copolymers, polybutylene terephthalate copolymerized with polytetramethylene glycol or isophthalic acid copolymerized polybutylene terephthalate is preferable as the polybutylene terephthalate copolymer (A1b).

The intrinsic viscosity of the polybutylene terephthalate copolymer (A1b) is preferably 0.5 to 2 dl / g. From the viewpoint of moldability and mechanical properties, those having an intrinsic viscosity in the range of 0.6 to 1.5 dl / g are more preferable. If the intrinsic viscosity is lower than 0.5 dl / g, the resulting resin composition tends to have a low mechanical strength. Moreover, if it is higher than 2 dl / g, the fluidity of the resin composition may be deteriorated and the moldability may be deteriorated or the laser weldability may be deteriorated.
The intrinsic viscosity is a value measured at 30 ° C. in a 1: 1 (mass ratio) mixed solvent of tetrachloroethane and phenol.

  The amount of the terminal carboxyl group of the polybutylene terephthalate copolymer (A1b) may be appropriately selected and determined, but is usually 60 eq / ton or less, preferably 50 eq / ton or less, and preferably 30 eq / ton or less. More preferably it is. If it exceeds 50 eq / ton, gas tends to be generated during melt molding of the resin composition. The lower limit value of the terminal carboxyl group amount is not particularly defined, but is usually 5 eq / ton.

  The amount of terminal carboxyl groups of the polybutylene terephthalate copolymer (A1b) is a value measured by titration using a 0.01 mol / l benzyl alcohol solution of sodium hydroxide by dissolving 0.5 g of resin in 25 mL of benzyl alcohol. is there. As a method for adjusting the amount of terminal carboxyl groups, a conventionally known arbitrary method such as a method for adjusting polymerization conditions such as a raw material charge ratio during polymerization, a polymerization temperature, a pressure reduction method, a method for reacting a terminal blocking agent, etc. Just do it.

  In the present invention, when the polybutylene terephthalate homopolymer (A1a) and the polybutylene terephthalate copolymer (A1b) are used in combination as the thermoplastic polyester resin material (A), the content of the polybutylene terephthalate copolymer (A1b) is (A1a). ) And (A1b), the polybutylene terephthalate copolymer (A1b) is preferably 5 to 95% by mass, more preferably 30 to 90% by mass, and still more preferably 40 to 90%, based on 100% by mass in total. It is mass%, Most preferably, it is 50-90 mass%. When the content of the polybutylene terephthalate copolymer (A1b) is less than 5% by mass, the laser transmittance and the laser welding strength are liable to be lowered, and when it exceeds 95% by mass, the moldability is liable to be lowered.

<Polycarbonate resin (A2a)>
(A) The polycarbonate resin (A2a) used for the thermoplastic polyester resin material may be branched heat obtained by reacting a dihydroxy compound or a small amount thereof with phosgene or a carbonic acid diester. It is a plastic polymer or copolymer. The production method of the polycarbonate resin is not particularly limited, and those produced by a conventionally known phosgene method (interfacial polymerization method) or melt method (transesterification method) can be used. The polycarbonate resin is preferable from the viewpoint of laser light transmittance and laser weldability.

  As the raw material dihydroxy compound, an aromatic dihydroxy compound is preferable, and 2,2-bis (4-hydroxyphenyl) propane (that is, bisphenol A), tetramethylbisphenol A, bis (4-hydroxyphenyl) -p-diisopropylbenzene, Hydroquinone, resorcinol, 4,4-dihydroxydiphenyl, etc. are mentioned, Preferably bisphenol A is mentioned. In addition, a compound in which one or more tetraalkylphosphonium sulfonates are bonded to the above aromatic dihydroxy compound can also be used.

  As the polycarbonate resin (A2a), among the above, aromatic polycarbonate resins derived from 2,2-bis (4-hydroxyphenyl) propane, or 2,2-bis (4-hydroxyphenyl) propane and other An aromatic polycarbonate copolymer derived from an aromatic dihydroxy compound is preferred. Further, it may be a copolymer such as a copolymer with a polymer or oligomer having a siloxane structure. Furthermore, you may mix and use 2 or more types of the polycarbonate resin mentioned above.

The viscosity average molecular weight of the polycarbonate resin (A2a) is preferably 5000 to 30000, more preferably 10,000 to 28000, and still more preferably 14,000 to 24,000. If a material having a viscosity average molecular weight lower than 5000 is used, the obtained welding member tends to have a low mechanical strength. On the other hand, if it is higher than 30000, the fluidity of the resin composition may be deteriorated and the moldability may be deteriorated or the laser weldability may be deteriorated.
The viscosity average molecular weight of the polycarbonate resin is a viscosity average molecular weight [Mv] converted from a solution viscosity measured at a temperature of 25 ° C. using methylene chloride as a solvent.

  The ratio (Mw / Mn) of the polystyrene-equivalent weight average molecular weight Mw and number average molecular weight Mn measured by gel permeation chromatography (GPC) of the polycarbonate resin (A2a) is 2 to 5. Preferably, 2.5-4 is more preferable. When Mw / Mn is too small, the fluidity in the molten state increases and the moldability tends to decrease. On the other hand, if Mw / Mn is excessively large, the melt viscosity tends to increase and molding becomes difficult.

  Further, the amount of terminal hydroxy groups of the polycarbonate resin (A2a) is preferably 100 ppm by mass or more, more preferably 200 ppm by mass or more, and still more preferably from the viewpoints of thermal stability, hydrolysis stability, color tone, and the like. It is 400 mass ppm or more, most preferably 500 mass ppm or more. However, it is usually 1500 mass ppm or less, preferably 1300 mass ppm or less, more preferably 1200 mass ppm or less, and most preferably 1000 mass ppm or less. When the amount of terminal hydroxy groups of the polycarbonate resin is too small, the laser transmittance tends to be lowered, and the initial hue at the time of molding may be deteriorated. When the amount of terminal hydroxy groups is excessively large, the residence heat stability and the moist heat resistance tend to decrease.

  (A) When the thermoplastic polyester resin material includes a polybutylene terephthalate homopolymer (A1a) and / or a polybutylene terephthalate copolymer (A1b) and a polycarbonate resin (A2a), the content of the polycarbonate resin (A2a) Is preferably 5 to 50% by mass, more preferably 10 to 45% by mass, and still more preferably 15 to 45% by mass with respect to a total of 100% by mass of (A1a), (A1b) and (A2a). %. When the content of the polycarbonate resin is less than 5% by mass, the laser light transmittance and the laser welding strength are likely to be lowered, and when it exceeds 50% by mass, the moldability may be lowered.

<Polyethylene terephthalate resin (A2b)>
(A) The polyethylene terephthalate resin (A2b) used for the thermoplastic polyester resin material is a resin whose main constituent unit is an oxyethyleneoxyterephthaloyl unit composed of terephthalic acid and ethylene glycol for all constituent repeating units. A repeating unit having a configuration other than the ethyleneoxyterephthaloyl unit may be included. The polyethylene terephthalate resin is produced using terephthalic acid or a lower alkyl ester thereof and ethylene glycol as main raw materials, but other acid components and / or other glycol components may be used together as raw materials.

Acid components other than terephthalic acid include phthalic acid, isophthalic acid, naphthalenedicarboxylic acid, 4,4′-diphenylsulfone dicarboxylic acid, 4,4′-biphenyldicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,3- Examples thereof include phenylenedioxydiacetic acid and structural isomers thereof, dicarboxylic acids such as malonic acid, succinic acid and adipic acid and derivatives thereof, and oxyacids such as p-hydroxybenzoic acid and glycolic acid or derivatives thereof.
Examples of diol components other than ethylene glycol include 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, aliphatic glycols such as pentamethylene glycol, hexamethylene glycol, and neopentyl glycol, cyclohexane Examples include alicyclic glycols such as dimethanol, and aromatic dihydroxy compound derivatives such as bisphenol A and bisphenol S.

  Further, the polyethylene terephthalate resin is a branched component, for example, trifunctional acid such as tricarballylic acid, trimellitic acid, trimellitic acid, etc., or tetrafunctional ester-like acid such as pyromellitic acid or glycerin, trimethylolpropane, pentane. An alcohol having a trifunctional or tetrafunctional ester-forming ability such as erythritol is copolymerized in an amount of 1.0 mol% or less, preferably 0.5 mol% or less, more preferably 0.3 mol% or less. There may be.

The intrinsic viscosity of the polyethylene terephthalate resin (A2b) is preferably 0.3 to 1.5 dl / g, more preferably 0.3 to 1.2 dl / g, and particularly preferably 0.4 to 0.8 dl / g. .
The intrinsic viscosity of the polyethylene terephthalate resin is a value measured at 30 ° C. in a 1: 1 (mass ratio) mixed solvent of tetrachloroethane and phenol.

Moreover, it is preferable that the density | concentration of the terminal carboxyl group of a polyethylene terephthalate resin (A2b) is 3-60 eq / ton, especially 5-50 eq / ton, Furthermore, it is preferable that it is 8-40 eq / ton. By setting the terminal carboxyl group concentration to 50 eq / ton or less, gas is less likely to be generated during melt molding of the resin material, and the mechanical properties of the obtained laser welding member tend to be improved. Is preferably 3 eq / ton or more, which tends to improve the heat resistance, residence heat stability, and hue of the laser welding member.
The terminal carboxyl group concentration of the polyethylene terephthalate resin can be obtained by dissolving 0.5 g of polyethylene terephthalate resin in 25 mL of benzyl alcohol and titrating with 0.01 mol / L benzyl alcohol solution of sodium hydroxide. Value.
As a method for adjusting the amount of terminal carboxyl groups, a conventionally known arbitrary method such as a method for adjusting polymerization conditions such as a raw material charge ratio during polymerization, a polymerization temperature, a pressure reduction method, a method for reacting a terminal blocking agent, etc. Just do it.

  (A) When the thermoplastic polyester resin material includes a polybutylene terephthalate homopolymer (A1a) and / or a polybutylene terephthalate copolymer (A1b) and a polyethylene terephthalate resin (A2b), the polyethylene terephthalate resin (A2b) is contained. The amount is preferably 5 to 50% by mass, more preferably 10 to 45% by mass, and still more preferably 15 to 100% by mass with respect to the total of 100% by mass of (A1a), (A1b) and (A2b). 45% by mass. When the content of the polyethylene terephthalate homopolymer is less than 5% by mass, the laser light transmittance and the laser welding strength are liable to be lowered, and when it exceeds 50% by mass, the moldability is liable to be lowered.

[(A) Other resins that can be used for thermoplastic polyester resin materials]
Moreover, (A) thermoplastic polyester-type resin material contains other thermoplastic resins other than above-mentioned (A1a), (A1b), (A2a), and (A2b) in the range which does not impair the effect of this invention. be able to. Specific examples of the other thermoplastic resins include polyacetal resins, polyphenylene oxide resins, polyphenylene sulfide resins, polysulfone resins, polyether sulfone resins, polyetherimide resins, polyether ketone resins, polyolefin resins, and the like. It is done.

[(D) Brominated flame retardant]
In the present invention, a brominated flame retardant may be contained as an essential component, and a phosphorus flame retardant or a nitrogen flame retardant may further be contained as another flame retardant.
The brominated flame retardant is not particularly limited as long as it has a bromine atom in the molecule. Preferred specific examples of the brominated flame retardant include brominated polycarbonate, brominated epoxy resin, brominated phenoxy. Resin, brominated polyphenylene ether resin, brominated polystyrene, brominated bisphenol A, glycidyl brominated bisphenol A, brominated benzyl polyacrylate, brominated imide (brominated phthalimide, etc.), among others, brominated polycarbonate, bromine Benzyl polyacrylate is more preferable because it has a flame retardant effect while suppressing a decrease in transmittance.

  Brominated benzyl (meth) acrylate is a polymer obtained by polymerizing benzyl (meth) acrylate containing a bromine atom alone, copolymerizing two or more kinds, or copolymerizing with other vinyl monomers. The bromine atom is preferably added to a benzene ring, and the number of addition is preferably 1 to 5, more preferably 4 to 5 per benzene ring.

  Examples of the benzyl acrylate containing a bromine atom include pentabromobenzyl acrylate, tetrabromobenzyl acrylate, tribromobenzyl acrylate, and mixtures thereof. Examples of the benzyl methacrylate containing a bromine atom include methacrylates corresponding to the acrylates described above.

  Specific examples of other vinyl monomers used for copolymerization with benzyl (meth) acrylates containing bromine atoms include acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, and benzyl acrylate. Acrylic acid esters, methacrylic acid, methyl methacrylate, ethyl methacrylate, butyl methacrylate, methacrylic acid esters such as benzyl methacrylate, unsaturated carboxylic acids such as styrene, acrylonitrile, fumaric acid, maleic acid, or anhydrides thereof, vinyl acetate And vinyl chloride.

  These are usually preferably used in an equimolar amount or less, particularly 0.5 times the molar amount or less with respect to benzyl (meth) acrylate containing a bromine atom.

  In addition, xylene diacrylate, xylene dimethacrylate, tetrabromoxylene diacrylate, tetrabromoxylene dimethacrylate, butadiene, isoprene, divinylbenzene, etc. can be used as vinyl monomers, and these usually contain bromine atoms. The benzyl acrylate or benzyl methacrylate can be used at a molar amount of 0.5 times or less.

  As brominated benzyl (meth) acrylate, pentabromobenzyl polyacrylate is preferred because of its high bromine content and high tracking resistance.

The brominated polystyrene preferably includes brominated polystyrene containing a repeating unit represented by the following general formula (1).
(In formula (1), t is an integer of 1 to 5, and n is the number of repeating units.)

  In the general formula (1), the CH group to which brominated benzene is bonded may be substituted with a methyl group. The brominated polystyrene may be a copolymer obtained by copolymerizing another vinyl monomer. Examples of the vinyl monomer in this case include styrene, α-methylstyrene, acrylonitrile, methyl acrylate, butadiene, and vinyl acetate. Moreover, brominated polystyrene may be used as a single substance or a mixture of two or more different structures, and may contain units derived from styrene monomers having different numbers of bromines in a single molecular chain.

  Specific examples of brominated polystyrene include, for example, poly (4-bromostyrene), poly (2-bromostyrene), poly (3-bromostyrene), poly (2,4-dibromostyrene), poly (2,6 -Dibromostyrene), poly (2,5-dibromostyrene), poly (3,5-dibromostyrene), poly (2,4,6-tribromostyrene), poly (2,4,5-tribromostyrene) , Poly (2,3,5-tribromostyrene), poly (4-bromo-α-methylstyrene), poly (2,4-dibromo-α-methylstyrene), poly (2,5-dibromo-α- Methyl (styrene), poly (2,4,6-tribromo-α-methylstyrene), poly (2,4,5-tribromo-α-methylstyrene) and the like, and poly (2,4,6-tribromostyrene). And poly (2,4,5-tribromostyrene) and polydibromostyrene and polytribromostyrene containing an average of 2 to 3 bromine groups in the benzene ring are particularly preferably used.

Brominated polystyrene is usually produced by brominating polystyrene. For example, it is produced by reacting bromine or bromine chloride with polystyrene in a chlorinated hydrocarbon solvent (for example, methylene chloride, dichloroethane, etc.) in the presence of a Lewis basic acid catalyst.
On the other hand, brominated styrene monomers (for example, 2,4-dibromostyrene, 2,6-dibromostyrene, 2,5-dibromostyrene, 3,5-dibromostyrene, 2,4,6-tribromostyrene, 2 , 4,5-tribromostyrene, 2,3,5-tribromostyrene, etc.).
The brominated polystyrene in the present invention may be any of the above bromination reaction or polymerization method, but there is a problem of bromination reaction other than the aromatic ring and the content of free bromine (atom or compound). Less bromine polystyrene (atomic or compound) generated in the subsequent heating and molding process is preferred, and brominated polystyrene by polymerization is more preferred.

In the brominated polystyrene, the number n (average polymerization degree) of the repeating units in the general formula (1) is preferably 30 to 1,500, more preferably 150 to 1,000, particularly 300 to 800. Is preferred. If the average degree of polymerization is less than 30, blooming tends to occur. On the other hand, if it exceeds 1,500, poor dispersion tends to occur and the mechanical properties tend to deteriorate. The mass average molecular weight (Mw) of brominated polystyrene is preferably about 10,000 to 200,000, more preferably 10,000 to 100,000, and still more preferably 10,000 to 70,000. It is.
In particular, in the case of the brominated product of polystyrene described above, the mass average molecular weight (Mw) is preferably 50,000 to 70,000, and in the case of brominated polystyrene by a polymerization method, the mass average molecular weight (Mw) is 10 It is preferable that it is about 3,000-30,000. In addition, a mass average molecular weight (Mw) can be calculated | required as a value of standard polystyrene conversion by GPC measurement.

  The brominated polycarbonate is preferably a brominated polycarbonate obtained from brominated bisphenol A, particularly tetrabromobisphenol A. Examples of the terminal structure include a 4-t-butylphenyl group and a 2,4,6-tribromophenyl group, and those having a 2,4,6-tribromophenyl group in the terminal group structure are particularly preferable.

  The average number of carbonate repeating units in the brominated polycarbonate may be appropriately selected and determined, but is usually 2 to 30. If the average number of carbonate repeating units is small, the molecular weight of the polyester resin may be lowered during melting. On the other hand, if it is too large, the melt viscosity of the polycarbonate becomes high, causing a dispersion failure in the molded product, which may deteriorate the appearance of the molded product, particularly the glossiness. Therefore, the average number of repeating units is preferably 3 to 15, particularly 3 to 10.

  The brominated polycarbonate obtained from the brominated bisphenol A can be obtained, for example, by an ordinary method in which brominated bisphenol and phosgene are reacted. Examples of the end-capping agent include aromatic monohydroxy compounds, which may be substituted with a halogen or an organic group.

As a brominated imide compound, Preferably, the compound shown by following General formula (2) is mentioned.
(In formula (2), i is an integer of 1 to 4.)
Among these, N, N′-ethylenebis (tetrabromophthalimide) in which i in the above formula (2) is 4 is preferable.

The brominated flame retardant (D) preferably has a bromine concentration of 52 to 75% by mass, and 56 to 7
It is more preferably 0% by mass, and further preferably 57-70% by mass. By setting the bromine concentration in such a range, it is easy to keep good flame retardancy.
The content of the brominated flame retardant is 2.5 to 100 parts by mass, preferably 5 to 80 parts by mass, more preferably 5 to 75 parts by mass with respect to 100 parts by mass of the (A) thermoplastic polyester resin material. Especially preferably, it is 5-40 mass parts. By adjusting the content of the brominated flame retardant to such a range, a resin composition for laser welding with high transmittance can be obtained.

<Other flame retardant: Phosphorus flame retardant>
As the phosphorus-based flame retardant, various commonly used phosphorus-based flame retardants can be used, but phosphate esters, phosphinates, phosphazenes, and reaction products of melamine and phosphoric acid are preferable.

  Examples of phosphate esters include trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri (2-ethylhexyl) phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tris (isopropylphenyl) phosphate, tris (Phenylphenyl) phosphate, trinaphthyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, diphenyl (2-ethylhexyl) phosphate, di (isopropylphenyl) phenyl phosphate, monoisodecyl phosphate, 2-acryloyloxyethyl acid phosphate, 2-Methacryloyloxyethyl acid phosphate, diphenyl-2-a Liloyloxyethyl phosphate, diphenyl-2-methacryloyloxyethyl phosphate, melamine phosphate, dimelamine phosphate, melamine pyrophosphate, triphenylphosphine oxide, tricresylphosphine oxide, diphenyl methanephosphonate, diethyl phenylphosphonate, resorcinol polyphenyl Condensed phosphate esters such as phosphate, resorcinol poly (di-2,6-xylyl) phosphate, bisphenol A polycresyl phosphate, biphenyl polycresyl phosphate, hydroquinone poly (2,6-xylyl) phosphate and condensates thereof; Can be mentioned. Examples of commercially available condensed phosphate esters include Daihachi Chemical Industry Co., Ltd., trade names PX-200, PX-201, PX-202, CR-733S, CR-741, and CR747.

  Phosphinates are phosphinates or diphosphinates, which are produced in aqueous solution using phosphinic acid and metal carbonates, metal hydroxides or metal oxides and are essentially monomeric compounds, Depending on the reaction conditions, polymeric phosphinates with a degree of condensation of 1-3 are also included depending on the environment.

  Specific examples of phosphinates include calcium dimethylphosphinate, magnesium dimethylphosphinate, aluminum dimethylphosphinate, zinc dimethylphosphinate, calcium ethylmethylphosphinate, magnesium ethylmethylphosphinate, aluminum ethylmethylphosphinate, ethylmethylphosphine Zinc oxide, calcium diethylphosphinate, magnesium diethylphosphinate, aluminum diethylphosphinate, zinc diethylphosphinate, calcium methyl-n-propylphosphinate, magnesium methyl-n-propylphosphinate, aluminum methyl-n-propylphosphinate, Zinc methyl-n-propylphosphinate, methandi (methylphosphinic acid) calcium, methandi (methylphosphite) Acid) magnesium methanedi (methylphosphinate) aluminum methanedi (methylphosphinate) zinc-1,4 (dimethyl phosphinic acid) calcium-1,4 (dimethyl phosphinic acid) magnesium.

  Benzene-1,4- (dimethylphosphinic acid) aluminum, benzene-1,4- (dimethylphosphinic acid) zinc, calcium methylphenylphosphinate, magnesium methylphenylphosphinate, aluminum methylphenylphosphinate, methylphenylphosphinic acid Examples include zinc, calcium diphenylphosphinate, magnesium diphenylphosphinate, aluminum diphenylphosphinate, and zinc diphenylphosphinate.

  Phosphazene is a compound having a structure in which a phosphorus atom and a nitrogen atom are connected by a double bond, and preferably a cyclic phenoxyphosphazene represented by the following general formula (I) and a chain represented by the following general formula (II) And at least one phenoxyphosphazene selected from the group consisting of the following general formula (I) and the following general formula (II) is crosslinked by a crosslinking group represented by the following general formula (III) Mention may be made of at least one compound selected from the group consisting of crosslinked phenoxyphosphazenes.

(In General Formula (I), m is an integer of 3 to 25, and Ph represents a phenyl group.)

(In the general formula (II), X ¹ represents a —N═P (OPh) 3 group or —N═P (O) OPh group, and Y ¹ represents a —P (OPh) 4 group or —P (O) (OPh) 2 group, n is an integer of 3 to 10,000, and Ph represents a phenyl group.)

(In the general formula (III), A is —C (CH ₃ ) ₂ —, —SO ₂ —, —S—, or —O—, and q is 0 or 1).

  Examples of the cyclic phenoxyphosphazene represented by the general formula (I) include hexachlorocyclophosphazene from a cyclic and linear chlorophosphazene mixture obtained by reacting ammonium chloride and phosphorus pentachloride at a temperature of 120 to 130 ° C. Phenoxycyclotriphosphazene, octaphenoxycyclotetraphosphazene, decaffenoxycyclopentaphosphazene, etc. obtained by taking out cyclic chlorophosphazenes such as triphosphazene, octachlorocyclotetraphosphazene, decachlorocyclopentaphosphazene and replacing them with phenoxy groups The compound of this is mentioned. The cyclic phenoxyphosphazene is preferably a compound in which m in the general formula (I) is an integer of 3 to 8.

  As the chain phenoxyphosphazene represented by the general formula (II), for example, hexachlorocyclotriphosphazene obtained by the above method is subjected to reduction polymerization at a temperature of 220 to 250 ° C., and the degree of polymerization obtained is 3 to 10, A compound obtained by substituting 000 linear dichlorophosphazenes with a phenoxy group. N in the general formula (II) of the linear phenoxyphosphazene is preferably 3 to 1,000, more preferably 3 to 100, and still more preferably 3 to 25.

  As the crosslinked phenoxyphosphazene, for example, hexachlorocyclotriphosphazene obtained by the above method is subjected to reduction polymerization at a temperature of 220 to 250 ° C., and the obtained linear dichlorophosphazene having a polymerization degree of 3 to 10,000 is converted into a phenoxy group. The compound obtained by substituting with is mentioned. N in the general formula (II) of the linear phenoxyphosphazene is preferably 3 to 1,000, more preferably 3 to 100, and still more preferably 3 to 25.

  Examples of the bridged phenoxyphosphazene include compounds having a crosslinked structure of 4,4′-sulfonyldiphenylene (bisphenol S residue) and compounds having a crosslinked structure of 2,2- (4,4′-diphenylene) isopropylidene group. A compound having a 4,4′-oxydiphenylene group cross-linking structure, a compound having a 4,4′-thiodiphenylene group cross-linking structure, and the like. Can be mentioned. The content of the phenylene group in the crosslinked phenoxyphosphazene is based on the number of all phenyl groups and phenylene groups in the cyclic phosphazene represented by the general formula (I) and / or the chain phenoxyphosphazene represented by the general formula (II). , Usually 50 to 99.9%, preferably 70 to 90%. The crosslinked phenoxyphosphazene is particularly preferably a compound having no free hydroxyl group in the molecule.

  Examples of the cyclic phenoxyphosphazene and the chain phenoxyphosphazene include H.I. R. Allcook, “Phosphorus-Nitrogen Compounds (Academic Press, (1972))”, J. Am. E. Mark, H.C. R. Allcook, R.A. It can be synthesized by the method described in “Inorganic Polymers (Prentice-Hall International, Inc. (1992))” by West.

  Examples of commercially available phosphazene compounds include Otsuka Chemical Co., Ltd., trade name SPS-100, Fushimi Pharmaceutical Co., Ltd., and Ravitor (registered trademark) FP-100.

  In the present invention, in addition to (D) bromine-based flame retardant, it is preferable to use a phosphorus-based flame retardant in combination. When a phosphorus-based flame retardant is used in combination, the content is (A) a thermoplastic polyester resin. Preferably it is 1-50 mass parts with respect to 100 mass parts of materials, More preferably, it is 5-40 mass parts, Especially it is 10-35 mass parts. However, the total of the brominated flame retardant and the phosphorus flame retardant is preferably within 100 parts by mass.

<Other flame retardant: Nitrogen-based flame retardant>
Examples of the nitrogen-based flame retardant include aliphatic amine compounds, aromatic amine compounds, nitrogen-containing heterocyclic compounds, cyanide compounds, aliphatic amides, aromatic amides, urea, thiourea and the like.
Examples of aliphatic amines include ethylamine, butylamine, diethylamine, ethylenediamine, butylenediamine, triethylenetetramine, 1,2-diaminocyclohexane, 1,2-diaminocyclooctane, and examples of aromatic amines include aniline and phenylenediamine. As nitrogen-containing heterocyclic compounds, uric acid, adenine, guanine, 2,6-diaminopurine, 2,4,6-triaminopyridine, triazine compounds, etc., as cyanide compounds, dicyandiamide, etc. as aliphatic amides are used. Includes N, N-dimethylacetamide and the like, and examples of the aromatic amide include N, N-diphenylacetamide and the like.

The triazine compounds exemplified above are nitrogen-containing heterocyclic compounds having a triazine skeleton, and are triazine, melamine, benzoguanamine, methylguanamine, cyanuric acid, melamine cyanurate, melamine isocyanurate, trimethyltriazine, triphenyltriazine, amelin, and amelide. , Thiocyanuric acid, diaminomercaptotriazine, diaminomethyltriazine, diaminophenyltriazine, diaminoisopropoxytriazine and the like.
As melamine cyanurate or melamine isocyanurate, an adduct of cyanuric acid or isocyanuric acid and a triazine compound is preferable, and usually an adduct having a composition of 1 to 1 (molar ratio), sometimes 1 to 2 (molar ratio). Can be mentioned.

Among nitrogen-based flame retardants, nitrogen-containing heterocyclic compounds are preferable, triazine compounds are preferable, and melamine cyanurate is more preferable.
When using a nitrogen-type flame retardant as a flame retardant, the content is preferably 0 to 50 parts by mass, more preferably 0 to 20 parts by mass with respect to 100 parts by mass of the (A) thermoplastic polyester resin material. Part, in particular 0 to 10 parts by weight.

[Antimony compound (E)]
The composition of the present invention may contain an antimony compound (E) that is a flame retardant aid.
Examples of the antimony compound (E) include an antimony compound (Sb ₂ O ₃ ), antimony pentoxide (Sb ₂ O ₅ ), and sodium antimonate. In particular, antimony trioxide is preferable from the viewpoint of impact resistance.

Content of an antimony compound (E) is 0-8 mass parts with respect to 100 mass parts of (A) thermoplastic polyester-type resin materials, More preferably, it is 0-7.5 mass parts, More preferably, it is 0- 5 parts by mass, particularly 0 to 4 parts by mass. If the above upper limit is exceeded, the transmittance is lowered, the crystallization temperature is lowered, the releasability is deteriorated, and mechanical properties such as impact resistance are lowered.
In addition, it is preferable to mix | blend an antimony compound (E) as a masterbatch with (A) polyester-type resin material, since an antimony compound can disperse | distribute uniformly in resin and the fall of the transmittance | permeability can be prevented.

<Anti-dripping agent>
In the present invention, it is also preferable to use an anti-dripping agent together with (D) the brominated flame retardant. As the anti-dripping agent, a fluoropolymer is preferable.
As the fluoropolymer, a known polymer having fluorine can be arbitrarily selected and used, and among these, a fluoroolefin resin is preferable.
As fluoroolefin resin, the polymer and copolymer containing a fluoroethylene structure are mentioned, for example. Specific examples thereof include difluoroethylene resin, tetrafluoroethylene resin, tetrafluoroethylene / hexafluoropropylene copolymer resin, and the like. Of these, tetrafluoroethylene resin and the like are preferable. As this fluoroethylene resin, a fluoroethylene resin having a fibril forming ability is preferable.
Examples of the fluoroethylene resin having a fibril-forming ability include Mitsui DuPont Fluorochemical Co., Ltd., Teflon (registered trademark) 6J, Daikin Chemical Industries, Ltd., Polyflon (registered trademark) F201L, and Polyflon F103.

  Examples of the aqueous dispersion of fluoroethylene resin include Teflon (registered trademark) 30J manufactured by Mitsui DuPont Fluorochemical Co., Ltd. and Fullon D-1 manufactured by Daikin Chemical Industries, Ltd. Furthermore, a fluoroethylene polymer having a multilayer structure formed by polymerizing vinyl monomers can also be used as the fluoropolymer. If the specific example is given, the metablene (trademark) A-3800 etc. by Mitsubishi Chemical Corporation will be mentioned.

  When a fluoropolymer is used as an anti-dripping agent, it is preferably 0-5 parts by mass, more preferably 0.1-3.0 parts by mass, more preferably 0.2 parts per 100 parts by mass of the (A) polyester resin material. It is preferable to contain -2.5 mass parts. If the fluoropolymer content is too small, the flame retardancy of the resin composition of the present invention may be insufficient. Conversely, if the content is too large, the molded product of the resin composition of the present invention may have poor appearance or mechanical properties. There is a possibility that a decrease in strength and a decrease in transmittance may occur.

[Other additives]
The laser welding resin composition of the present invention can be blended with various additives as desired. Such additives include, for example, reinforcing fillers, impact modifiers, flow modifiers, auxiliary colorants, dispersants, stabilizers, plasticizers, UV absorbers, light stabilizers, antioxidants, charging Examples thereof include inhibitors, lubricants, mold release agents, crystal accelerators, crystal nucleating agents, and epoxy compounds.

The reinforcing filler that can be contained in the resin composition of the present invention has an effect of improving the mechanical properties of the resin composition obtained by blending with the resin, and a conventional inorganic filler for plastics is used. be able to. Preferably, fibrous fillers such as glass fiber, carbon fiber, basalt fiber, wollastonite and potassium titanate fiber can be used. In addition, granular or amorphous fillers such as calcium carbonate, titanium oxide, feldspar minerals, clays, organic clays, glass beads, etc .; plate-like fillers such as talc; scaly forms such as glass flakes, mica and graphite A filler can also be used. Among these, it is preferable to use a fibrous filler, particularly glass fiber, from the viewpoints of laser light transmittance, mechanical strength, rigidity, and heat resistance. As the glass fiber, either a round sectional shape or an irregular sectional shape can be used.
More preferably, the reinforcing filler is surface-treated with a surface treatment agent such as a coupling agent. The glass fiber to which the surface treatment agent is attached is preferable because it is excellent in durability, heat and humidity resistance, hydrolysis resistance, and heat shock resistance.

  As the surface treatment agent, any conventionally known one can be used. Specifically, for example, silane coupling agents such as amino silane, epoxy silane, allyl silane, and vinyl silane are preferable. Among these, aminosilane-based surface treatment agents are preferable, and specifically, for example, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, and γ- (2-aminoethyl) aminopropyltrimethoxysilane are preferable. Take as an example.

Other examples of the surface treatment agent include a novolac type epoxy resin surface treatment agent, a bisphenol A type epoxy resin surface treatment agent, and the like, and a treatment with a novolac type epoxy resin surface treatment agent is particularly preferable.
The silane-based surface treatment agent and the epoxy resin-based surface treatment agent may be used singly or in combination, and it is also preferable to use both in combination.

The glass fiber is preferably a glass fiber having an anisotropic cross-sectional shape in which the ratio of the major axis to the minor axis in the cross section is 1.5 to 10 from the viewpoints of laser weldability and heat shock resistance. The cross-sectional shape is preferably one having a rectangular or oval cross section, and a major axis / minor axis ratio of 2.5 to 8, more preferably 3 to 6. When the major axis is D ₂ , the minor axis is D ₁ , and the average fiber length is L, the aspect ratio ((L × 2) / (D ₂ + D ₁ )) is preferably 10 or more. When such flat glass fibers are used in this way, the warpage of the molded product is suppressed, which is particularly effective when manufacturing a box-shaped welded body.

  The content of the reinforcing filler is preferably 5 to 150 parts by mass with respect to 100 parts by mass of the (A) thermoplastic polyester resin material. When the content of the reinforcing filler is less than 5 parts by mass, sufficient strength and heat resistance are difficult to obtain, and when it exceeds 150 parts by mass, fluidity and laser weldability tend to be lowered. The more preferable content of the reinforcing filler is 15 to 130 parts by mass, more preferably 20 to 120 parts by mass, and particularly preferably 30 to 100 parts by mass.

  The impact modifier that can be contained in the resin composition of the present invention functions to improve the heat shock resistance of the resin composition. The impact resistance improver is not particularly limited as long as it has the effect of improving the impact resistance of the resin, but polyester elastomer, styrene elastomer, polyolefin elastomer, acrylic elastomer, polyamide elastomer, polyurethane elastomer. , Fluorine-based elastomers, silicone-based elastomers, acrylic core / shell type elastomers and the like are known, and polyester-based elastomers and styrene-based elastomers are preferable.

  The polyester elastomer is a thermoplastic polyester having rubber properties at room temperature, preferably a thermoplastic elastomer mainly composed of a polyester block copolymer, and has a high melting point and high crystallinity as a hard segment. A block copolymer having an amorphous polyester or an amorphous polyether as a soft segment is preferable. The content of the soft segment of the polyester-based elastomer is at least 20 to 95 mol% in all segments, and in the case of a block copolymer of polybutylene terephthalate and polytetramethylene glycol (PBT-PTMG copolymer), 50 to 95 mol%. The content of the preferred soft segment is 50 to 90 mol%, particularly 60 to 85 mol%. Among these, a polyester ether block copolymer, particularly a PTMG-PBT copolymer, is preferable because a decrease in transmittance is reduced.

  Specific examples of polyester elastomers include “Primalloy” (trade name, registered trademark (hereinafter the same)) manufactured by Mitsubishi Chemical Corporation, “Perprene” (manufactured by Toyobo Co., Ltd.), “Hytrel” (manufactured by Toray DuPont), “ “Byron” (manufactured by Toyobo Co., Ltd.), “Polyester” (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) and the like are preferred.

Moreover, as a styrene-type elastomer, it consists of a styrene component and an elastomer component, and what contains a styrene component normally in the ratio of 5-80 mass%, Preferably it is 10-50 mass%, Especially 15-30 mass% is preferable. Examples of the elastomer component at this time include conjugated diene hydrocarbons such as butadiene, isoprene and 1,3-pentadiene. More specifically, a copolymer of styrene and butadiene (SBS) elastomer, styrene and Examples thereof include a copolymer (SIS) elastomer with isoprene.
It is also preferable to use a resin (SEBS, SEPS) obtained by hydrogenating the above SBS elastomer or SIS elastomer.

  Specific examples of styrene elastomers include “Dynalon” (manufactured by JSR, trade name and registered trademark (hereinafter the same)), “Tuftec” (manufactured by Asahi Kasei Chemicals), “Hibler”, “Septon” (manufactured by Kuraray) Etc.

Further, as an impact resistance improver, a copolymer-type elastomer containing an epoxy group is also preferable because it has good reactivity with a thermoplastic polyester resin such as polybutylene terephthalate and the laser transmittance is hardly lowered.
The type of copolymer elastomer containing an epoxy group is not limited. For example, those obtained by introducing an epoxy group into the above-described styrene elastomer, polyolefin elastomer, acrylic elastomer and the like are preferable. For example, in the case of a styrene-butadiene copolymer obtained by copolymerizing polystyrene as a hard segment and butadiene as a soft segment, an epoxy group-containing elastomer can be obtained by epoxidizing an unsaturated double bond portion of a diene component.
In addition, the olefin-based elastomer only needs to have a polyolefin portion in the soft phase, and ethylene propylene rubber such as EPR and EPDM can be preferably used.
The method for introducing an epoxy group is not particularly limited, and it may be incorporated into the main chain, or a polymer containing an epoxy group may be introduced into the olefin elastomer in a block or graft form. Preferably, a (co) polymer having an epoxy group is introduced in a graft form.

  Specific examples of copolymer-type elastomers containing epoxy groups include “Bond First” (trade name, registered trademark (hereinafter the same)) manufactured by Sumitomo Chemical Co., Ltd., “Rotada” (manufactured by Arkema), “Elvalloy” (Mitsui DuPont Polychemical Co., Ltd., “Paraloid” (Rohm and Haas Co., Ltd.), “Metabrene” (Mitsubishi Chemical Co., Ltd.), “Epofriend” (Daicel Chemical Industries Co., Ltd.), and the like.

  The impact resistance improver may be used alone or in combination of two or more. The content of the impact modifier is 0 to 20 parts by weight, preferably 1 to 18 parts by weight, more preferably 2 to 15 parts by weight, and still more preferably, with respect to 100 parts by weight of the (A) thermoplastic polyester resin material. It is 3-12 mass parts, Most preferably, it is 3-7 mass parts. If the content of the impact resistance improver exceeds 20 parts by mass, the heat resistance rigidity tends to decrease.

The epoxy compound that can be contained in the resin composition of the present invention functions to improve the laser weldability and heat-and-moisture resistance properties of the resin composition, and to further improve the strength and durability of the weld part of the molded product.
The epoxy compound is not particularly limited as long as it has one or more epoxy groups in one molecule, and is usually a glycidyl compound which is a reaction product of alcohol, phenol or carboxylic acid and epichlorohydrin, or an olefinic compound. A compound obtained by epoxidizing a heavy bond may be used.
Preferable specific examples of the epoxy compound include, for example, bisphenol type epoxy compounds such as bisphenol A type epoxy compounds and bisphenol F type epoxy compounds, resorcin type epoxy compounds, novolac type epoxy compounds, alicyclic compound type diepoxy compounds, glycidyl ethers, Examples thereof include glycidyl esters and epoxidized polybutadiene.
Examples of the alicyclic compound type epoxy compound include vinylcyclohexene dioxide and dicyclopentadiene oxide.

Specific examples of glycidyl ethers include monoglycidyl ethers such as methyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, decyl glycidyl ether, stearyl glycidyl ether, phenyl glycidyl ether, butylphenyl glycidyl ether, and allyl glycidyl ether; Examples include pentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, glycerin diglycidyl ether, propylene glycol diglycidyl ether, and bisphenol A diglycidyl ether.
Examples of glycidyl esters include monoglycidyl esters such as benzoic acid glycidyl ester and sorbic acid glycidyl ester; adipic acid diglycidyl ester, terephthalic acid diglycidyl ester, orthophthalic acid diglycidyl ester, and the like.

  The epoxy compound may be a copolymer having a glycidyl group-containing compound as one component. For example, a copolymer of a glycidyl ester of α, β-unsaturated acid and one or more monomers selected from the group consisting of α-olefin, acrylic acid, acrylic ester, methacrylic acid, and methacrylic ester Can be mentioned.

The epoxy compound is preferably an epoxy compound having an epoxy equivalent of 100 to 500 g / eq and a number average molecular weight of 2000 or less. When the epoxy equivalent is less than 100 g / eq, since the amount of the epoxy group is too large, the viscosity of the resin composition is increased, and the adhesiveness of the weld portion is likely to be reduced. On the contrary, when the epoxy equivalent exceeds 500 g / eq, the amount of the epoxy group decreases, and thus the effect of improving the heat and moisture resistance of the resin composition tends not to be sufficiently exhibited. When the number average molecular weight exceeds 2000, the compatibility with the (A) thermoplastic polyester resin material tends to decrease, and the mechanical strength of the molded product tends to decrease.
As the epoxy compound, a bisphenol A type epoxy compound or a novolac type epoxy compound obtained from a reaction of bisphenol A or novolak with epichlorohydrin is particularly preferable.

  Although content of an epoxy compound is 0-5 mass parts with respect to 100 mass parts of (A) thermoplastic polyester-type resin materials, it is preferable to make it contain 0.1 mass part or more in order to express an effect. If the content is more than 3 parts by mass, crosslinking may proceed and the fluidity at the time of molding may be deteriorated, so 0.2 to 3 parts by mass, particularly 0.2 to 2 parts by mass is preferable.

  Examples of the flow modifier that can be contained in the resin composition of the present invention include styrene oligomers, olefin oligomers, acrylic oligomers, polyfunctional compounds, branched polymers (dendrimers (dendritic polymers), highly branched types, hyper-types). Branched and cyclic oligomers are included), and the like is preferably exemplified and plays a role of imparting fluidity and maintaining mechanical strength. In particular, when a box-shaped welded body or a welded body having a flow length of 70 mm or more is produced, the addition of a flow modifier is effective.

As the stabilizer that can be contained in the resin composition of the present invention, a phosphorus stabilizer, a sulfur stabilizer, and a phenol stabilizer are preferable.
Particularly preferred is a phenol-based stabilizer. When the resin composition contains a polyethylene terephthalate resin or a polycarbonate resin, it is preferable to use a phenol-based stabilizer and a phosphorus-based stabilizer in combination.
Examples of the phosphorus stabilizer include phosphorous acid, phosphoric acid, phosphite ester, phosphate ester, etc. Among them, organic phosphate compounds, organic phosphite compounds, or organic phosphonite compounds are preferable.

The organic phosphate compound is preferably the following general formula:
(R ¹ O) _3-n P (═O) OH _n (1)
(In formula (1), R < ¹ > is an alkyl group or an aryl group, and they may be the same or different. N represents an integer of 0 to 2). More preferably, R ¹ is a long-chain alkyl acid phosphate compound having 8 to 30 carbon atoms. Specific examples of the alkyl group having 8 to 30 carbon atoms include octyl group, 2-ethylhexyl group, isooctyl group, nonyl group, isononyl group, decyl group, isodecyl group, dodecyl group, tridecyl group, isotridecyl group, tetradecyl group, hexadecyl group Group, octadecyl group, eicosyl group, triacontyl group and the like.

  Examples of the long-chain alkyl acid phosphate include octyl acid phosphate, 2-ethylhexyl acid phosphate, decyl acid phosphate, lauryl acid phosphate, octadecyl acid phosphate, oleyl acid phosphate, behenyl acid phosphate, phenyl acid phosphate, nonyl phenyl acid phosphate Acid phosphate, phenoxyethyl acid phosphate, alkoxy polyethylene glycol acid phosphate, bisphenol A acid phosphate, dimethyl acid phosphate, diethyl acid phosphate, dipropyl acid phosphate, diisopropyl acid phosphate, dibutyl acid phosphate, geo Chill acid phosphate, di-2-ethylhexyl acid phosphate, dioctyl acid phosphate, dilauryl acid phosphate, distearyl acid phosphate, diphenyl acid phosphate, and a bis-nonylphenyl acid phosphate, or the like. Among these, octadecyl acid phosphate is preferable.

The organic phosphite compound is preferably the following general formula:
^{R 2 O-P (OR 3} ) (OR 4) ··· (2)
(In the formula (2), R ² , R ³ and R ⁴ are each a hydrogen atom, an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms, and R ² , R ³ and R ⁴ are At least one of which is an aryl group having 6 to 30 carbon atoms.).

  Examples of the organic phosphite compound include triphenyl phosphite, tris (nonylphenyl) phosphite, dilauryl hydrogen phosphite, triethyl phosphite, tridecyl phosphite, tris (2-ethylhexyl) phosphite, and tris (tridecyl). ) Phosphite, tristearyl phosphite, diphenyl monodecyl phosphite, monophenyl didecyl phosphite, diphenyl mono (tridecyl) phosphite, tetraphenyldipropylene glycol diphosphite, tetraphenyltetra (tridecyl) pentaerythritol tetraphosphite Hydrogenated bisphenol A phenol phosphite polymer, diphenyl hydrogen phosphite, 4,4′-butylidene-bis (3-methyl-6-t rt-butylphenyldi (tridecyl) phosphite), tetra (tridecyl) 4,4′-isopropylidenediphenyldiphosphite, bis (tridecyl) pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, di Lauryl pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, tris (4-tert-butylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, hydrogenated bisphenol A pentaerythritol phosphite Phytopolymer, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite Phosphite, 2,2'-methylenebis (4,6-di -tert- butylphenyl) octyl phosphite, bis (2,4-dicumylphenyl) pentaerythritol diphosphite and the like. Among these, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite is preferable.

The organic phosphonite compound is preferably the following general formula:
R ⁵ -P (OR ⁶ ) (OR ⁷ ) (3)
(In the formula ^(6), R 5, ^{R 6} and ^{R 7} are each a hydrogen atom, an alkyl group or an aryl group having 6 to 30 carbon atoms having 1 to 30 carbon ^atoms, R 5, ^{R 6} and ^{R 7} At least one of which is an aryl group having 6 to 30 carbon atoms.).

  Examples of the organic phosphonite compound include tetrakis (2,4-di-iso-propylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,4-di-n-butylphenyl) -4,4′-biphenyl. Range phosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,4'-biphenylene diphosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,3'-biphenylene diphospho Knight, tetrakis (2,4-di-tert-butylphenyl) -3,3'-biphenylenediphosphonite, tetrakis (2,6-di-iso-propylphenyl) -4,4'-biphenylenediphosphonite, Tetrakis (2,6-di-n-butylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2, -Di-tert-butylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,3'-biphenylenediphosphonite, and tetrakis (2,6- And di-tert-butylphenyl) -3,3′-biphenylenediphosphonite.

  As the sulfur stabilizer, any conventionally known sulfur atom-containing compound can be used, and among these, thioethers are preferred. Specifically, for example, didodecylthiodipropionate, ditetradecylthiodipropionate, dioctadecylthiodipropionate, pentaerythritol tetrakis (3-dodecylthiopropionate), thiobis (N-phenyl-β-naphthylamine) ), 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, tetramethylthiuram monosulfide, tetramethylthiuram disulfide, nickel dibutyldithiocarbamate, nickel isopropylxanthate, trilauryltrithiophosphite. Among these, pentaerythritol tetrakis (3-dodecylthiopropionate) is preferable.

  Examples of the phenol-based stabilizer include pentaerythritol tetrakis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate), octadecyl-3- (3,5-di-tert-butyl-4) -Hydroxyphenyl) propionate, thiodiethylenebis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate), pentaerythritol tetrakis (3- (3,5-di-neopentyl-4-hydroxyphenyl) ) Propionate) and the like. Among these, pentaerythritol tetrakis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate), octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) ) Propionate is preferred.

  One type of stabilizer may be contained, or two or more types may be contained in any combination and ratio.

  The content of the stabilizer is preferably 0.001 to 2 parts by mass with respect to 100 parts by mass of the (A) thermoplastic polyester resin material. When the content of the stabilizer is less than 0.001 part by mass, it is difficult to expect an improvement in the thermal stability and compatibility of the resin composition, and a decrease in molecular weight and hue deterioration during molding are likely to occur. When it exceeds, it will become excess amount and there exists a tendency for generation | occurrence | production of silver and a hue deterioration to occur further easily. The content of the stabilizer is more preferably 0.001 to 1.8 parts by mass, and still more preferably 0.1 to 1.5 parts by mass.

  As the release agent that can be contained in the resin composition of the present invention, known release agents that are usually used for polyester resins can be used. Among them, polyolefin compounds, fatty acid ester compounds, and silicone compounds can be used. One or more mold release agents selected are preferred.

  Examples of the polyolefin compound include compounds selected from paraffin wax and polyethylene wax. Among them, those having a mass average molecular weight measured by GPC of 700 to 10000, more preferably 900 to 8000 are preferable. In addition, a modified polyolefin compound in which a hydroxyl group, a carboxyl group, a hydroxyl group, an epoxy group or the like is introduced into the side chain is particularly preferable.

  Examples of the fatty acid ester compounds include fatty acid esters such as glycerin fatty acid esters, sorbitan fatty acid esters, and pentaerythritol fatty acid esters, and partially saponified products thereof. Among them, carbon number is 11 to 28, preferably carbon number 17 Fatty acid esters composed of ~ 21 fatty acids are preferred. Specific examples include glycerol monostearate, glycerol monobehenate, glycerol dibehenate, glycerol-12-hydroxy monostearate, sorbitan monobehenate, pentaerythritol distearate, pentaerythritol tetrastearate and the like.

  Moreover, as a silicone type compound, the compound modified | denatured from points, such as compatibility with a polyester resin, is preferable. Examples of the modified silicone oil include silicone oil in which an organic group is introduced into the side chain of polysiloxane, silicone oil in which an organic group is introduced into both ends and / or one end of polysiloxane, and the like. Examples of the organic group to be introduced include an epoxy group, an amino group, a carboxyl group, a carbinol group, a methacryl group, a mercapto group, and a phenol group, and preferably an epoxy group. As the modified silicone oil, a silicone oil in which an epoxy group is introduced into the side chain of polysiloxane is particularly preferable.

  It is preferable that content of a mold release agent is 0.05-2 mass parts with respect to 100 mass parts of (A) thermoplastic polyester-type resin materials. If the amount is less than 0.05 parts by mass, the surface property tends to decrease due to poor mold release at the time of melt molding, while if it exceeds 2 parts by mass, the kneading workability of the resin composition decreases, Cloudiness may be seen on the surface of the molded product. The content of the release agent is preferably 0.07 to 1.5 parts by mass, more preferably 0.1 to 1.0 parts by mass.

As a manufacturing method of the resin composition of this invention, it can carry out in accordance with the conventional method of resin composition preparation. Usually, the components and various additives added as desired are mixed together and then melt-kneaded in a single or twin screw extruder. Further, the resin composition of the present invention can also be prepared without mixing each component in advance or by mixing only a part of the components in advance and supplying them to an extruder using a feeder and melt-kneading them. Further, (A) a master batch is prepared by melt-kneading a mixture of a part of the resin constituting the thermoplastic polyester resin material with a part of the other resin, and then the remaining polyester resin or other These components may be blended and melt-kneaded.
In addition, when using fibrous reinforcement fillers, such as glass fiber, it is also preferable to supply from the side feeder in the middle of the cylinder of an extruder.

  The heating temperature at the time of melt kneading can be appropriately selected from the range of usually 220 to 300 ° C. If the temperature is too high, decomposition gas is likely to be generated, which may cause opacity. Therefore, it is desirable to select a screw configuration in consideration of shear heat generation. In order to suppress decomposition during kneading or molding in the subsequent process, it is desirable to use an antioxidant or a heat stabilizer.

[Laser welded compact]
The manufacturing method of a molded object is not specifically limited, The molding method generally employ | adopted about the polyester resin composition can be employ | adopted arbitrarily. For example, injection molding method, ultra-high speed injection molding method, injection compression molding method, two-color molding method, hollow molding method such as gas assist, molding method using heat insulating mold, rapid heating mold were used. Molding method, foam molding (including supercritical fluid), insert molding, IMC (in-mold coating molding) molding method, extrusion molding method, sheet molding method, thermoforming method, rotational molding method, laminate molding method, press molding method, Examples thereof include blow molding, and injection molding is particularly preferable.

The resin composition for laser welding of the present invention preferably has an absorbance a _0.75 (absorbance converted to a thickness of 0.75 mm) of the molded product before laser welding of 0.05 to _1.5. More preferably, it is 0.08-1.0. By adjusting this value, the spread of the resin melt in laser welding (size of the melt pool) can be adjusted. For this reason, practically sufficient welding strength can be obtained also in butt welding. In addition, the width of laser welding processability is widened at the time of superposition welding and butt welding because of excellent gap weldability.
The absorbance “a” can be adjusted by the alloy type of the base resin, the addition of additives such as an elastomer and a reinforcing material, and the amount of nigrosine. Further, at the time of forming a molded body, it is possible to adjust by adjusting molding conditions such as the degree of the mold surface, the distance from the gate, the injection rate, the surface progression coefficient, and the mold temperature.
Absorbance a _0.75 at a thickness of 0.75 mm is determined by using a UV-visible near-infrared spectrophotometer (“UV-3100PC” manufactured by Shimadzu Corporation), a transmittance T at a wavelength of 940 nm of a molded product having a thickness of 0.75 mm. _0.75 (%) and reflectance R _0.75 (%) are obtained, and the values are used to obtain the following equation.
Absorbance a _0.75 = −log {T _0.75 / (100−R _0.75 )}
Incidentally, when measured using a molded plate thickness is not 0.75mm, using the transmittance _{T t} and the reflectance _{R t} measurement part of the wall thickness _{t (mm), 0.75 × a} t / t As a value converted to a thickness of 0.75 mm.

In the laser welding resin composition of the present invention, the incidence rate K _0.75 of the molded body having a thickness of 0.75 mm before laser welding is preferably in the range of 15 to 80%, more preferably 25 to 75%. Yes, particularly preferably in the range of 30-70%.
When the incidence rate is less than 20%, the butt welding performance is lowered and the gap welding performance is also lowered. On the other hand, when the incidence rate exceeds 80%, the welding performance is lowered due to the overlapping, and the gap welding performance is also lowered.
Since the incident light rate K _{0.75 is set} to such a range, the amount of laser light transmitted and the amount of laser light absorbed are adjusted, so that a molding made of a laser light transmissive resin as in conventional laser welding. It is not necessary to use two types of molded body made of a body and a laser light absorbing resin, and it becomes possible to provide a polyester-based laser welded molded body capable of laser welding with only one type of resin material. In particular, the effect of the present invention is remarkable when welding welds made of the same kind of resin material are welded together.

As a method for adjusting the incidence rate, it is preferable to use a resin composition having a crystallization temperature (Tc) of 190 ° C. or lower. That is, the incidence rate can be adjusted to a preferred range by controlling the crystallization temperature (Tc) to be low.
Note that the incidence rate varies greatly depending on the transmittance of the laser beam. Molding conditions can be cited as factors that change the transmittance. Examples of molding conditions include injection rate, mold temperature, resin temperature, and pressure holding. Above all, it tends to change depending on the injection rate and mold temperature. Also, the mold structure is likely to change depending on the mold surface property, gate shape, gate position, and number of gates. Furthermore, in the molded body, it varies greatly depending on the part where the transmittance is measured and the distance from the gate position at the time of molding. Therefore, the incident rate can be adjusted to a preferable range by appropriately determining these conditions.

  The crystallization temperature (Tc) is preferably 188 ° C. or lower, more preferably 185 ° C. or lower, further preferably 182 ° C. or lower, and particularly preferably 180 ° C. or lower. Moreover, the minimum is 130 degreeC normally, Preferably it is 140 degreeC or more. The crystallization temperature (Tc) is measured by DSC. The details are as described in the examples.

The laser welding resin composition of the present invention is molded into a laser welding member having a desired shape by an injection molding method. As the injection molding method, for example, a high-speed injection molding method, an injection compression molding method, or the like can be used.
The injection molding conditions are not particularly limited, but the injection speed is preferably 10 to 500 mm / sec, more preferably 30 to 400 mm / sec, still more preferably 50 to 300 mm / sec, particularly 80 to 200 mm / sec. preferable.
Note that the faster the emission speed, the higher the transmittance, which affects the incidence rate. However, if the injection speed is too high, gas burning occurs at the flow end of the molded body, so it is preferable to take measures such as reducing the injection speed to an appropriate injection speed or increasing the size of the gas vent in the mold structure.

Moreover, 250-280 degreeC is preferable and, as for resin temperature, 255-275 degreeC is more preferable. The mold temperature is preferably 40 to 130 ° C, more preferably 50 to 100 ° C.
The lower the mold temperature, the higher the transmittance, which in turn affects the incidence rate. If the mold temperature is too low, the degree of crystallinity of the molded product will be low, resulting in increased post-shrinkage and deterioration in dimensional stability. It is also preferable to adjust the mold temperature.

  The shape of the laser welded molded body is arbitrary, and it may be a deformed extruded product (bar, pipe, etc.) that is used for welding by abutting the end, and a current-carrying part that requires particularly high waterproofness and airtightness, A metal-inserted molded product used for electronic parts and the like is also preferable.

[Laser welded body]
When the molded body made of the resin composition for laser welding according to the present invention is used, it is not necessary to use two types of molded bodies made of a laser light-transmitting resin and a molded body made of a laser light-absorbing resin. . In addition, since the penetration depth of the laser beam is large, so that a large melting depth can be secured, not only the overlap welding but also the butt welding between the ends of the laser welding molded body, which has not been possible so far, is sufficient. High weld strength can be achieved. In addition, even when a gap is generated in the joining portion due to sink marks or warpage during molding, the gap is 0.1 mm or more, preferably 0.2 mm or more, more preferably 0.5 mm or more, and particularly 0. Laser welding is possible even when the thickness is 8 mm or more.
The type of laser light to be irradiated is arbitrary as long as it is near-infrared laser light. YAG (yttrium, aluminum, garnet crystal) laser (wavelength 1064 nm), LD (laser diode) laser (wavelength 808 nm, 820 nm, 840 nm, 880 nm) , 940 nm) and the like can be preferably used.

  The shape, size, thickness, etc. of the welded body that has been laser-welded are arbitrary. Applications of the welded body include parts for transportation equipment such as automobiles, parts for electrical and electronic equipment, parts for industrial machinery, and other consumer parts. Is preferred.

Preferred examples of the laser welding method include butt welding and superposition welding.
In the butt welding, as shown in FIG. 2, the two molded bodies 1 and 2 are butted and irradiated with the laser beam 4 while being scanned, so that a welded portion 5 is generated, whereby a laser welded body is formed.

  As shown in FIG. 3, the superposition welding is performed by superimposing and scanning the two molded bodies 1 and 2 and irradiating the laser beam 4 while scanning to form a welded portion 5, thereby forming a laser welded body. .

  The molded body obtained with the colored resin composition of the present invention is abutted or overlapped and laser-welded, so that the obtained laser-welded body has considerably improved welding strength and is required for the laser-welded body. Meet practical strength. Also, considering the laser welding conditions, it can be seen that the allowable range of the energy amount by the laser light has a much wider range, and the compact that can cope with such wide laser welding conditions has a complicated structure. It is possible to provide laser welding with high practicality for welding of molded bodies of the above, welding of molded bodies having changed thickness, and the like. Further, it is a laser welded body having a function of suppressing heat discoloration and colorant bleeding, and having little influence on electronic components.

  EXAMPLES Next, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.

  The colorant production examples 1 to 3 are shown below, and Table 1 shows the composition ratios and the like.

(Colorant Production Example 1: Production of Colorant Example 1)
0.66 parts by mass of anthraquinone dye C1 (maximum absorption wavelength 628 nm CI Solvent Blue 104), 0.58 parts by mass of perinone dye C2 (maximum absorption wavelength 472 nm CI Solvent Red 179) and anthraquinone dye C3 (maximum absorption) Wavelength 446 nm CI Solvent Yellow 163) 0.56 parts by mass was put into a blender and stirred for 5 hours to obtain 1.8 parts by mass of Colorant Example 1.

The absorbance and maximum absorption wavelength of the dye used above were measured by the following method, and the absorption curve is shown in FIG.
[Method of measuring absorbance and maximum absorption wavelength of dye]
0.05 g of a dye sample is weighed, dissolved in dimethylformamide (DMF), and adjusted in a 100 ml volumetric flask. Next, 2 ml of the adjustment liquid was measured with a whole pipette and diluted with a DMF in a 50 ml volumetric flask to prepare an adjustment liquid.
The absorption liquid was measured for the obtained adjustment liquid using the ultraviolet visible spectrophotometer (The brand name: UV-1100 by Shimadzu Corporation Corp.).

(Colorant Production Examples 2-3: Production of Colorant Example 2 and Comparative Colorant Example 1)
In Production Examples 2 to 3, Colorant Example 2 and Comparative Colorant Example 1 were obtained in the same manner as Production Example 1 except that the composition of Production Example 1 was changed to the composition described in Table 1.

(Manufacture of molded products and laser welding using the molded products)
Using any of the colorant examples produced above, a molded body made of the resin composition was produced by the method described below. Thereafter, laser welding was performed using the molded body.
In addition, the used raw materials other than a coloring agent are each component of the following Table 2.

(Examples 1-17, Comparative Examples 1-5)
[Manufacture of laser welded body for overlay welding]
Each component and nigrosine (NUBIAN BLACK TH-807) described in Tables 1 and 2 were blended in the amounts (all parts by mass) described in Tables 3 to 4, and this was blended with a 30 mm vent type twin screw extruder ( The glass fiber is supplied from the seventh side feeder from the hopper, the extruder barrel set temperature C1 to C15 is 260 ° C, the die is 250 ° C, and the screw is rotated. The mixture was kneaded under the conditions of several 200 rpm and a discharge rate of 40 kg / hour and extruded into a strand shape to obtain resin composition pellets.
In Comparative Example 4, since the bulk specific gravity of the flame retardant was small and the blending concentration was high, feeding was not possible and pellets could not be obtained.

The crystallization temperature (Tc) of the resin composition was increased from 30 to 300 ° C. at a rate of temperature increase of 20 ° C./min using a differential scanning calorimetry (DSC) machine (“Pyris Diamond” manufactured by Perkin Elmer). After being held at 300 ° C. for 3 minutes, it was measured as the peak top temperature (unit: ° C.) of the exothermic peak observed when the temperature was lowered at a temperature lowering rate of 20 ° C./min.
It is considered that the lower the crystallization temperature (Tc), the slower the solidification, and the higher the laser welding strength and the weld strength.

[Optical properties: measurement of transmittance, reflectance and converted absorbance]
After drying the resin composition pellet obtained above at 120 ° C. for 5 hours, using an injection molding machine (NEX80-9E, manufactured by Nissei Plastic Industry Co., Ltd.), cylinder temperature 260 ° C., mold temperature 80 ° C., thickness 0 Plates of .75 mm and 60 mm square were manufactured under conditions of an injection speed of 75 mm / sec.
On the opposite gate side of the plate having a thickness of 0.75 mm and a thickness of 60 mm, a transmittance T _0.75 (%) at a wavelength of 940 nm using an ultraviolet visible near infrared spectrophotometer (“UV-3100PC” manufactured by Shimadzu Corporation). And reflectance R _0.75 (%). Furthermore, the absorbance a _0.75 having a thickness of 0.75 mm is obtained.
was determined by the equation _{a 0.75 = -log {T 0.75 /} (100-R 0.75)}.
[How to find the incidence rate]
Incidence rate _K0.75 (unit:%) was calculated _| required with the following formula | equation.
Incidence factor K _0.75 (%) = 100−T _0.75 −R _0.75
Incident rate _K0.75 is an incident rate with respect to the laser beam of wavelength 940nm when a molded object is 0.75mm thick.

  The resin composition pellets obtained above were dried at 120 ° C. for 5 hours, and then an injection molding machine (manufactured by Nissei Plastic Industry Co., Ltd., NEX80-9E) was used at a cylinder temperature of 255 ° C. and a mold temperature of 65 ° C. An ASTM No. 4 dumbbell piece having a thickness of 0 mm was produced under the condition of an injection speed of 100 mm / sec.

Laser weldability (overlap welding of dumbbell pieces, gap welding strength):
Two dumbbells 11 and 12 of ASTM No. 4 having the same composition obtained above were used, and a laser welding apparatus manufactured by Fine Devices (laser wavelength: 940 nm, laser spot diameter: Φ2.1 mm, laser head and test piece) 4), the ends of the dumbbell 11 and the dumbbell 12 opposite to the resin injection gate (on the opposite gate side) are overlapped with each other as shown in FIG. A piece 14 with metal piece spacers 15 and 15 'sandwiched between them is placed on a glass base (not shown), a glass plate 16 is placed on the dumbbells 11 and 12, and 0.1 MPa is applied from above. While pressing, the laser beam 17 is irradiated under the conditions of a laser output of 50 to 70 W, a laser scanning speed of 10 mm / sec, and a laser scanning distance of 16 mm. It was welded. At that time, the gap between the metal spacers 15 and 15 ′ is changed to 0.0 mm to 0.6 mm described in Tables 3 to 4, and using an Instron 5544 universal testing machine, Under the conditions of 160 mm and a tensile speed of 5 mm / min, a load (unit: N) for breaking by applying a load in the pulling direction indicated by the arrow a in FIG.
In addition, the weldability is not only high in welding strength, but also maintaining high welding strength under any conditions means that the laser welding conditions are wide and excellent in laser welding properties. It is evaluated.

Flame retardancy (UL94):
A combustion test piece having a cylinder temperature of 250 ° C. and a thickness of 0.75 mm was prepared from the pellets obtained above using an injection molding machine (SE-50, manufactured by Sumitomo Heavy Industries, Ltd.).
According to the method of Subject 94 (UL94) of Underwriters Laboratories,
Flame retardancy was tested using five test pieces (thickness: 0.75 mm), and classified into V-0, V-1, V-2, and HB. V-0 has the highest flame retardancy.
The results are listed in Tables 3 to 4 below.

  The resin composition for laser welding of the present invention has extremely excellent laser welding processability in addition to high colorability and flame retardancy. Therefore, since the resin composition of the present invention can be suitably and widely applied to automobile parts, electrical / electronic equipment parts, and other materials, industrial applicability is very high.

Claims (13)

A resin composition used for welding by laser light,
(A) For 100 parts by mass of a thermoplastic polyester resin material containing a polybutylene terephthalate homopolymer and / or a polybutylene terephthalate copolymer,
(B) Nigrosine 0.0005 to 0.5 parts by mass,
(C) 0.01-2 parts by weight of a colorant containing an anthraquinone dye, and
(D) A laser welding resin composition comprising 2.5 to 100 parts by mass of a brominated flame retardant.   (C) The colorant includes a perinone dye C2 having a maximum absorption wavelength in the range of 460 to 480 nm and an anthraquinone dye C1 in which the maximum absorption wavelength is in the range of 590 to 635 nm, and the mass ratio C2 / C1 between the two is 0.4 to The resin composition for laser welding according to claim 1, wherein the resin composition is a colorant contained in a ratio of 2. 3.   (A) The thermoplastic polyester resin material includes a polybutylene terephthalate homopolymer and a polybutylene terephthalate copolymer, and the content of the polybutylene terephthalate copolymer is 5 to 95% by mass with respect to 100% by mass in total of both. The resin composition for laser welding according to claim 1 or 2.   (A) The thermoplastic polyester resin material includes a polybutylene terephthalate homopolymer and a polyethylene terephthalate resin, and the content of the polyethylene terephthalate resin is 5 to 50% by mass with respect to 100% by mass of both. Laser welding resin composition in any one of 1-3.   (A) The thermoplastic polyester-based resin material contains a polybutylene terephthalate homopolymer and a polycarbonate resin, and the content of the polycarbonate resin is 5 to 50 mass with respect to a total of 100 mass% of the polybutylene terephthalate homopolymer and the polycarbonate resin. The resin composition for laser welding according to claim 1 or 2, wherein the composition is%.   (D) The brominated flame retardant is brominated acrylate, The resin composition for laser welding according to any one of claims 1 to 5. The absorbance a _0.75 (absorbance converted to a molded plate having a thickness of 0.75 mm) with respect to 940 nm laser light of the molded plate made of the resin composition is 0.05 to _1.5 . The laser welding resin composition according to any one of the above. The incidence rate _K0.75 (incidence rate converted into a thickness of 0.75 mm) of the molded plate made of the resin composition with respect to 940 nm laser light is 15 to 80%. The resin composition for laser welding according to claim 1.
However, the incidence rate K _0.75 is calculated as follows using the transmittance T _0.75 and the reflectance R _0.75 at a thickness of _0.75 mm.
Incidence factor K _0.75 (%) = 100−T _0.75 −R _0.75   A molded article for laser welding comprising the resin composition for laser welding according to claim 1.   A laser welded product of the molded product according to claim 9.   The laser welded body according to claim 10, wherein a gap between the formed bodies when the welded body is welded is at least 0.1 mm in at least a part of the welded portion.   The laser welded body according to claim 10 or 11, wherein the molded bodies are butt-welded to each other.   The laser welded body according to claim 10 or 11, wherein the molded bodies are laminated and welded together.