Title of the invention: Method for producing polyamide resin composition, molded product thereof, and laser welded product
Technical field
[0001]
　The present invention relates to a polyamide resin composition, a molded product thereof, and a method for producing a laser welded product.
Background technology
[0002]
　A laser welding method is known as one of the methods for joining thermoplastic resin members to each other. The features of the laser welding method are that welding can be performed without bringing the laser light generating part into contact with the part to be welded, that the heat effect on the peripheral part is negligible due to local heating, and that mechanical vibration There is no risk, welding of fine parts and members with a three-dimensional and complicated structure is possible, high reproducibility, high airtightness can be maintained, welding strength is relatively high, welded parts It is difficult to see the boundary between the two, and dust is not generated.
[0003]
　As a laser welding method, a first resin member that is weakly absorable to laser light and a second resin member that is absorptive to laser light are superposed, and laser light is emitted through the first resin member. Is disclosed, and a method for welding these is disclosed (see, for example, Patent Document 1). Specifically, as the first resin member, a resin composition containing polyamide 6 and a modified ethylene / α-olefin copolymer (additive having weak absorption to laser light) is used. As the second resin member, a resin composition containing polyamide 6 and 0.3% by weight of carbon black (additive that absorbs laser light) is used.
[0004]
　Further, as a laser welding resin composition, a resin composition containing a polyamide resin, a polycarbonate resin, and a filler such as glass fiber is disclosed (see, for example, Patent Document 2).
Prior art literature
Patent documents
[0005]
Patent Document 1: Japanese Patent Application Laid-Open No. 2004-148800
Patent Document 2: Japanese Patent Application Laid-Open No. 2006-273992
Outline of the invention
Problems to be solved by the invention
[0006]
　However, since the first resin member and the second resin member shown in Patent Document 1 do not contain a filler or the like, their mechanical strength and rigidity are not sufficient. Therefore, the welded products of these resin members are not suitable for applications that require high mechanical strength and rigidity.
[0007]
　Further, even with the resin composition described in Patent Document 2, there is a problem that the laser transmittance is not sufficient and it is difficult to obtain sufficient laser weldability. In addition, the amount of the filler compounded in the resin composition was small, and the mechanical strength and rigidity were not sufficient. Further, if the blending amount of the filler is increased in order to increase the mechanical strength and rigidity, there are problems that the laser transmittance and the appearance of the molded product are likely to deteriorate.
[0008]
　The present invention has been made in view of the above circumstances, and has high laser welding property, high mechanical strength, and high heat resistance that can exhibit good welding strength at the time of laser welding without lowering the transmittance of laser light. It is an object of the present invention to provide a polyamide resin composition having a property and a method for producing a laser welded body using the same.
Means to solve problems
[0009]
　[1] The polyamide resin (A) having a melting point of 300 ° C. or higher measured by a differential scanning calorimeter (DSC) is 30 to 89.9 parts by mass, and the melting point measured by the differential scanning calorimetry (DSC) is substantially the same. Includes 0 to 45 parts by mass of the polyamide resin (B), 0.1 to 5 parts by mass of the light transmissive dye (C), and 10 to 55 parts by mass of the fibrous filler (D). It is a polyamide resin composition (however, the total of (A), (B), (C) and (D) is 100 parts by mass), and the polyamide resin (A) is a component unit derived from a dicarboxylic acid. The component unit (a1) derived from the dicarboxylic acid, which includes (a1) and the component unit (a2) derived from the diamine, is based on 100 mol% of the total component unit (a1) derived from the dicarboxylic acid. , 20 to 100 mol% of the component unit derived from terephthalic acid, 0 at least one of the component unit derived from an aromatic dicarboxylic acid other than terephthalic acid and the component unit derived from an aliphatic dicarboxylic acid having 4 to 20 carbon atoms. The component unit (a2) containing ~ 80 mol% and derived from the diamine is a component unit derived from an aliphatic diamine having 4 to 15 carbon atoms and a component unit derived from an alicyclic diamine having 4 to 20 carbon atoms. The amount of heat of fusion (ΔH) of the polyamide resin composition measured by a differential scanning calorimeter (DSC), which contains at least one of the above, is measured by the amount other than the fibrous filler (D) with respect to the total mass of the polyamide resin composition. the total mass of the obtained by dividing by the ratio correction amount of heat of fusion of the components ([Delta] H R ) is 10 ~ 70 J / g, the moldings of the polyamide resin composition, of a laser beam having a wavelength of 940nm in thickness 1.6mm A polyamide resin composition having a permeability of 15% or more.
　[2] The component unit (a2) derived from the diamine is a component unit derived from the aliphatic diamine having 4 to 15 carbon atoms with respect to a total of 100 mol% of the component unit (a2) derived from the diamine. The polyamide resin composition according to [1], which comprises 50 to 100 mol%.
　[3] The polyamide resin according to [2], wherein the component unit derived from the aliphatic diamine having 4 to 15 carbon atoms includes a component unit derived from a linear aliphatic diamine having 4 to 8 carbon atoms. Composition.
　[4] The polyamide resin composition according to [3], wherein the component unit derived from the linear aliphatic diamine having 4 to 8 carbon atoms is a component unit derived from an alkylene diamine having 4 to 8 carbon atoms. Stuff.
　[5] The polyamide resin composition according to [4], wherein the component unit derived from the alkylenediamine having 4 to 8 carbon atoms is a component unit derived from 1,6-hexanediamine.
　[6] The polyamide resin composition according to any one of [1] to [5], wherein the component unit derived from the dicarboxylic acid (a1) further contains a component unit derived from isophthalic acid.
　[7] The polyamide resin (B) contains a component unit (b1) derived from a dicarboxylic acid and a component unit (b2) derived from a diamine, and the component unit (b1) derived from the dicarboxylic acid is isophthalic acid. The component unit derived from the diamine (b2) containing a component unit derived from an acid is any one of [1] to [6] including a component unit derived from an aliphatic diamine having 4 to 15 carbon atoms. The polyamide resin composition described.
　[8] The component unit derived from the dicarboxylic acid (b1) may further contain a component unit derived from terephthalic acid, and the component unit derived from the isophthalic acid and the component unit derived from the terephthalic acid. The polyamide resin composition according to [7], wherein the molar ratio is 55/45 to 100/0 (molar ratio) of the component unit derived from the isophthalic acid / the component unit derived from the terephthalic acid.
　[9] The content of the fibrous filler (D) is 40 parts by mass or less based on 100 parts by mass of the total of (A), (B), (C) and (D). [1] The polyamide resin composition according to any one of [8].
　[10] A light-transmitting resin composition for laser welding, which comprises the polyamide resin composition according to any one of [1] to [9].
　[11] A molded product obtained by molding the polyamide resin composition according to any one of [1] to [9].
　[12] A step of molding the polyamide resin composition according to any one of [1] to [9] to obtain a first molded product, and a light-absorbing resin composition containing a thermoplastic resin and a light-absorbing dye. The step of obtaining a second molded body obtained by molding an object, the first molded body and the second molded body are superposed, and laser light is irradiated through the first molded body to perform the first molding. A method for producing a laser-welded body, which comprises a step of welding the body and the second molded body.
　[13] The method for producing a laser welded body according to [12], wherein the thermoplastic resin is a polyamide resin.
　[14] The method for producing a laser welded body according to [13], wherein the polyamide resin is the same as the polyamide resin (A) contained in the polyamide resin composition.
Effect of the invention
[0010]
　According to the present invention, a polyamide resin composition having high laser weldability, high mechanical strength and high heat resistance that can exhibit good welding strength at the time of laser welding without lowering the transmission rate of laser light can be obtained. Can be provided. According to the method for producing a laser welded body using a molded body of such a polyamide resin composition, a laser welded body having a high welding strength can be imparted.
A brief description of the drawing
[0011]
[Fig. 1] Fig. 1 is a schematic diagram showing a method for measuring welding strength.
Mode for carrying out the invention
[0012]
　The present inventors, include a specific polyamide resin (A) and light transmitting dye (C), and the correction amount of heat of fusion ([Delta] H R ) polyamide resin composition which is adjusted, the fibrous filler (D) It has been found that even if a relatively large amount is contained, good welding intensity can be exhibited at the time of laser welding without significantly reducing the transparency to laser light. As a result, it has been found that the polyamide resin composition can exhibit good welding strength at the time of laser welding while having good mechanical strength and heat resistance.
[0013]
　The reason for this is not clear, but it is presumed as follows. In order to laser weld the molded bodies with high welding strength (bonding strength), it is usually desired to sufficiently melt the resin by the energy of the laser beam in the welded portion to form a large molten portion.
　On the other hand, the specific polyamide resin (A) and the light-transmitting dye (C) contained in the polyamide resin composition of the present invention are relatively easy to transmit laser light. As a result, the polyamide resin composition can maintain good laser light transmittance even if it contains the fibrous filler (D). Further, since the polyamide resin composition contains the polyamide resin (A) whose crystallinity is appropriately adjusted and the polyamide resin (B) having low crystallinity as needed, the corrected calorific value of melting of the polyamide resin composition ( [Delta] H R ) is adjusted appropriately low enough not to impair the mechanical strength and heat resistance. That is, the energy required to melt the crystal portion is reduced. As a result, it is considered that the resin can be sufficiently melted even if the irradiation energy of the laser beam is small, so that a large molten portion can be easily formed and a high welding strength (bonding strength) can be easily obtained.
[0014]
　Correction heat of fusion of the polyamide resin composition ([Delta] H R ) is a polyamide resin or appropriately low crystallinity of (A), the crystallinity is relatively high the polyamide resin (A) and the crystalline relatively low polyamide It can be adjusted by combining with the resin (B) or increasing the content of the fibrous filler (D). The present invention has been made based on such findings.
[0015]
　1. 1. Polyamide resin composition The polyamide resin composition of the
　present invention contains a polyamide resin (A), a polyamide resin (B), a light-transmitting dye (C), and a fibrous filler (D).
[0016]
　1-1. Polyamide resin (A) The
　polyamide resin (A) is a polyamide resin whose melting point (Tm) is measured by a differential scanning calorimeter (DSC). The melting point (Tm) of the polyamide resin (A) measured by a differential scanning calorimeter (DSC) is preferably 300 to 340 ° C. When the melting point (Tm) of the polyamide resin (A) is 300 ° C. or higher, it is easy to impart high heat resistance to the molded product, and when it is 340 ° C. or lower, it is not necessary to raise the molding temperature excessively. It is possible to suppress thermal decomposition of resin and other components during molding. The melting point of the polyamide resin (A) is more preferably 300 to 330 ° C.
[0017]
　The glass transition temperature (Tg) measured by the differential scanning calorimeter (DSC) of the polyamide resin (A) is preferably 80 to 150 ° C, more preferably 90 to 135 ° C.
[0018]
　The melting point (Tm) and glass transition temperature (Tg) of the polyamide resin (A) can be measured with a differential scanning calorimeter (for example, DSC220C type, manufactured by Seiko Instruments Inc.). The specific measurement conditions may be the same as in the examples described later.
[0019]
　The melting point (Tm) and the glass transition temperature (Tg) of the polyamide resin (A) can be adjusted by, for example, the composition of the component unit (a1) derived from the dicarboxylic acid described later. In order to raise the melting point of the polyamide resin (A), for example, the content ratio of the component unit derived from terephthalic acid may be increased.
[0020]
　The heat of fusion (ΔH) measured by differential scanning calorimetry (DSC) of the polyamide resin (A) is preferably more than 5 J / g. The amount of heat of fusion is an index of the crystallinity of the resin, and the larger the amount of heat of fusion, the higher the crystallinity. When the heat of fusion (ΔH) of the polyamide resin (A) exceeds 5 J / g, the crystallinity is high, so that the heat resistance and mechanical strength of the obtained molded product can be increased. The polyamide resin (A) preferably exhibits crystallinity.
[0021]
　The heat of fusion (ΔH) is a value obtained according to JIS K7122. That is, the heat of fusion (ΔH) is obtained from the area of ​​the exothermic peak associated with crystallization in the differential scanning calorimetry chart obtained by scanning at a temperature rise rate of 10 ° C./min by differential scanning calorimetry (DSC). .. The heat of fusion (ΔH) is a value in the first heating process that does not erase the history.
[0022]
　The polyamide resin (A) contains a component unit (a1) derived from a dicarboxylic acid and a component unit (a2) derived from a diamine.
[0023]
　[Component unit derived from dicarboxylic acid (a1)] The
　component unit derived from dicarboxylic acid (a1) preferably contains at least a component unit derived from terephthalic acid. The polyamide resin (A) containing a component unit derived from terephthalic acid has high crystallinity and can impart good heat resistance and mechanical strength (tensile strength, rigidity) to the molded product.
[0024]
　Specifically, the component unit (a1) derived from dicarboxylic acid includes 20 to 100 mol% of component unit derived from terephthalic acid, 0 to 80 mol% of component unit derived from aromatic dicarboxylic acid other than terephthalic acid, and It is more preferable to contain at least one of 0 to 40 mol% of the component unit derived from the aliphatic dicarboxylic acid having 4 to 20 carbon atoms, 55 to 100 mol% of the component unit derived from terephthalic acid, and other than terephthalic acid. It is more preferable to contain 0 to 45 mol% of a component unit derived from an aromatic dicarboxylic acid. However, the total amount of the component units (a1) derived from the dicarboxylic acid is 100 mol%.
[0025]
　Examples of terephthalic acid include terephthalic acid and terephthalic acid esters (alkyl esters of terephthalic acid having 1 to 4 carbon atoms).
[0026]
　Examples of aromatic dicarboxylic acids other than terephthalic acid include isophthalic acid, 2-methylterephthalic acid, naphthalenedicarboxylic acid and esters thereof, preferably isophthalic acid.
[0027]
　The aliphatic dicarboxylic acid having 4 to 20 carbon atoms is preferably an aliphatic dicarboxylic acid having 6 to 12 carbon atoms, and examples thereof include malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, and adipic acid. , 2-Methyladipic acid, trimethyladipic acid, pimeric acid, 2,2-dimethylglutaric acid, 3,3-diethylsuccinic acid, azelaic acid, sebacic acid, suberic acid and the like, preferably adipic acid. ..
[0028]
　The molar ratio of the component unit derived from terephthalic acid to the component unit derived from an aromatic dicarboxylic acid (preferably isophthalic acid) other than terephthalic acid in the component unit derived from dicarboxylic acid (a1) is derived from terephthalic acid. Component unit / Component unit derived from an aromatic dicarboxylic acid (preferably isophthalic acid) other than terephthalic acid = 55/45 to 80/20, more preferably 60/40 to 85/15. When the amount of the component unit derived from terephthalic acid is a certain amount or more, the heat resistance and mechanical strength of the obtained molded product can be easily increased. When the amount of the component unit derived from terephthalic acid is a certain amount or less, it is easy to reduce the irradiation energy of the laser light required for laser welding in the obtained molded product.
[0029]
　The component unit derived from the dicarboxylic acid (a1) may further contain a component unit derived from the alicyclic dicarboxylic acid as long as the effects of the present invention are not impaired. Examples of the alicyclic dicarboxylic acid include 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid and the like.
[0030]
　[Component unit derived from diamine (a2)] The
　component unit derived from diamine (a2) is a component unit derived from an aliphatic diamine having 4 to 15 carbon atoms and an alicyclic diamine having 4 to 20 carbon atoms. Contains at least one of the derived component units.
[0031]
　The component unit derived from the aliphatic diamine having 4 to 15 carbon atoms preferably contains the component unit derived from the linear aliphatic diamine having 4 to 8 carbon atoms.
[0032]
　The linear aliphatic diamine having 4 to 8 carbon atoms is more preferably a linear aliphatic diamine having 6 to 8 carbon atoms. Examples of linear aliphatic diamines having 4 to 8 carbon atoms include 1,4-diaminobutane, 1,6-hexanediamine, 1,7-diaminoheptane, and 1,8-octanediamine. Includes 4-8 linear alkylenediamines. Of these, 1,6-hexanediamine is preferable. Only one type of component unit derived from the linear aliphatic diamine having 4 to 8 carbon atoms may be contained, or two or more types may be contained.
[0033]
　The component unit derived from the aliphatic diamine having 4 to 15 carbon atoms may further include the component unit derived from the branched aliphatic diamine having 4 to 15 carbon atoms. Examples of branched aliphatic diamines having 4 to 15 carbon atoms include 2-methyl-1,8-octanediamine and 2-methyl-1,5-pentanediamine. Such a branched aliphatic diamine can appropriately lower the crystallinity of the polyamide resin (A). Therefore, the correction amount of heat of fusion ([Delta] H of the polyamide resin composition R was moderately lower),
[0034]
　Examples of alicyclic diamines having 4 to 20 carbon atoms include 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, 1,3-bis (aminomethyl) cyclohexane, and 1,4-bis (aminomethyl). Cyclohexane, isophorone diamine, piperazine, 2,5-dimethylpiperazin, bis (4-aminocyclohexyl) methane, bis (4-aminocyclohexyl) propane, 4,4'-diamino-3,3'-dimethyldicyclohexylpropane, 4, 4'-diamino-3,3'-dimethyldicyclohexylmethane, 4,4'-diamino-3,3'-dimethyl-5,5'-dimethyldicyclohexylmethane, 4,4'-diamino-3,3'-dimethyl -5,5'-Dimethyldicyclohexylpropane, α, α'-bis (4-aminocyclohexyl) -p-diisopropylbenzene, α, α'-bis (4-aminocyclohexyl) -m-diisopropylbenzene, α, α' -Bis (4-aminocyclohexyl) -1,4-cyclohexane, α, α'-bis (4-aminocyclohexyl) -1,3-cyclohexane and the like are included. Of these, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, bis (aminomethyl) cyclohexane, bis (4-aminocyclohexyl) methane, and 4,4'-diamino-3,3'-dimethyldicyclohexylmethane are preferable; More preferred are 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, bis (4-aminocyclohexyl) methane, 1,3-bis (aminocyclohexyl) methane, and 1,3-bis (aminomethyl) cyclohexane.
[0035]
　The total content of the component unit derived from the aliphatic diamine having 4 to 15 carbon atoms and the component unit derived from the alicyclic diamine having 4 to 20 carbon atoms (preferably for the aliphatic diamine having 4 to 15 carbon atoms). The content of the derived component unit) is preferably 50 mol% or more with respect to the total amount of the component unit (a2) derived from the diamine. When the total content is 50 mol% or more, the water resistance of the obtained molded product tends to increase. Total content of component units derived from aliphatic diamines having 4 to 15 carbon atoms and component units derived from aliphatic diamines having 4 to 20 carbon atoms (preferably linear fats having 4 to 8 carbon atoms). The content of the group diamine component unit) is more preferably 70 mol% or more, further preferably 90 mol% or more, and may be 100 mol%. However, the total amount of the component units (a2) derived from diamine is 100 mol%.
[0036]
　The component unit derived from diamine (a2) may further contain a component unit derived from another diamine as long as the effect of the present invention is not impaired. Examples of other diamines include aromatic diamines. Examples of aromatic diamines include metaxylylenediamine and the like. The content of the component unit derived from other diamines may be 50 mol% or less, preferably 40 mol% or less, based on the total amount of the component units (a2) derived from diamine.
[0037]
　In a specific example of the polyamide resin (A), the component unit (a1) derived from a dicarboxylic acid is a component unit derived from terephthalic acid and a component unit derived from isophthalic acid, and is derived from a linear aliphatic diamine. Resins whose component units are 1,6-diaminohexane; component units derived from dicarboxylic acid (a1) are component units derived from terephthalic acid and component units derived from adipic acid, and are linear aliphatic diamines. A resin or the like in which the component unit derived from is 1,6-diaminohexane is included. Only one type of the polyamide resin (A) may be contained, or two or more types may be contained.
[0038]
　The ultimate viscosity [η] of the polyamide resin (A) measured in 96.5% sulfuric acid at a temperature of 25 ° C. is preferably 0.7 to 1.6 dl / g, preferably 0.8 to 1.2 dl. It is more preferably / g. When the ultimate viscosity [η] of the polyamide resin (A) is at least a certain level, the strength of the molded product tends to be sufficiently increased. When the ultimate viscosity [η] is below a certain level, the fluidity of the resin composition during molding is not easily impaired. The ultimate viscosity [η] is adjusted by the molecular weight of the polyamide resin (A).
[0039]
　The ultimate viscosity of the polyamide resin (A) is prepared by dissolving 0.5 g of the polyamide resin (A) in 50 ml of a 96.5% sulfuric acid solution to prepare a sample solution. The number of seconds of flow of the sample liquid can be measured using an Ubbelohde viscometer under the condition of 25 ± 0.05 ° C., and the obtained value can be calculated by applying the following formula.
　[Η] = ηSP / [C (1 + 0.205ηSP)]
[0040]
　In the above equation, each algebra or variable represents:
　[Η]: Extreme viscosity (dl / g)
　ηSP: Specific viscosity
　C: Sample concentration (g / dl)
[0041]
　ηSP is calculated by the following formula.
　ηSP = (t-t0) / t0
　t: Number of seconds for sample solution to flow (seconds)
　t0: Number of seconds for blank sulfuric acid to flow (seconds)
[0042]
　From the viewpoint of thermal stability during compounding and molding, the polyamide resin (A) may have at least some of the terminal groups of the molecules sealed with a terminal sealant. The amount of the terminal amino group of the polyamide resin (A) is preferably 0.1 to 300 mmol / kg, more preferably 20 to 300 mmol / kg, and even more preferably 35 to 200 mmol / kg.
[0043]
　The amount of terminal amino groups can be measured by the following method. 1 g of polyamide resin is dissolved in 35 mL of phenol, and 2 mL of methanol is mixed to prepare a sample solution. Then, using thymol blue as an indicator, titration was performed on the sample solution using a 0.01-defined HCl aqueous solution from blue to yellow, and the amount of terminal amino groups ([NH 2 ], unit: mmol / kg) is measured.
[0044]
　The polyamide resin (A) can be produced by the same method as a known polyamide resin, and can be produced, for example, by polycondensing a dicarboxylic acid and a diamine in a uniform solution. Specifically, a low-order condensate is obtained by heating a dicarboxylic acid and a diamine in the presence of a catalyst as described in International Publication No. 03/085029, and then this low-order condensate is obtained. It can be produced by applying shear stress to the melt and polycondensing it.
[0045]
　When adjusting the ultimate viscosity of the polyamide resin (A), it is preferable to add an end-capping agent (molecular weight adjusting agent) to the reaction system. The end sealant can be, for example, a monocarboxylic acid or a monoamine. Examples of monocarboxylic acids include aliphatic monocarboxylic acids having 2 to 30 carbon atoms, aromatic monocarboxylic acids and alicyclic monocarboxylic acids. These terminal sealants can adjust the molecular weight of the polyamide resin (A) and the amount of terminal amino groups of the polyamide resin (A). The aromatic monocarboxylic acid and the alicyclic monocarboxylic acid may have a substituent at the cyclic structure portion.
[0046]
　Examples of aliphatic monocarboxylic acids include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecylic acid, myristic acid, palmitic acid, stearic acid, oleic acid and linoleic acid. Is done. Examples of aromatic monocarboxylic acids include benzoic acid, toluic acid, naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid and phenylacetic acid. Examples of alicyclic monocarboxylic acids include cyclohexanecarboxylic acids.
[0047]
　The terminal sealant is added to the reaction system of the dicarboxylic acid and the diamine. The amount of addition is preferably 0.07 mol or less, more preferably 0.05 mol or less, based on 1 mol of the total amount of dicarboxylic acids. By using the molecular weight adjusting agent in such an amount, at least a part thereof is incorporated into the polyamide, whereby the ultimate viscosity [η] of the polyamide resin (A) can be easily adjusted within a desired range.
[0048]
　The content of the polyamide resin (A) is 30 to 89 when the total of the polyamide resin (A), the polyamide resin (B), the light-transmitting dye (C) and the fibrous filler (D) is 100 parts by mass. It is preferably 9.9 parts by mass. When the content of the polyamide resin (A) is 30 parts by mass or more, the mechanical strength and heat resistance of the molded product can be easily increased, and when it is 89.9 parts by mass or less, the irradiation of laser light required for welding the molded product It is easy to reduce energy. The content of the polyamide resin (A) is 40 to 85 when the total of the polyamide resin (A), the polyamide resin (B), the light-transmitting dye (C) and the fibrous filler (D) is 100 parts by mass. It is more preferably parts by mass, and even more preferably 60 to 85 parts by mass.
[0049]
　The content of the polyamide resin (A) is preferably 85.7 to 99.9 parts by mass when the total of the polyamide resin (A) and the polyamide resin (B) is 100 parts by mass. By setting the content of the polyamide resin (A) in the above range, the transmittance of the laser light can be further increased, and a molded product having good laser weldability can be easily obtained. As described above, a molded product having a high laser light transmittance and excellent laser welding property is preferably used as a light transmitting resin member in laser welding. From the above viewpoint, the content of the polyamide resin (A) is more preferably 90 to 99.9 parts by mass when the total of the polyamide resin (A) and the polyamide resin (B) is 100 parts by mass.
[0050]
　1-2. Polyamide resin (B) The
　polyamide resin (B) is a polyamide resin whose melting point (Tm) is substantially not measured by a differential scanning calorimeter (DSC). Such polyamide resin (B), since crystallinity reasonably low, corrected heat of fusion ([Delta] H of the polyamide resin composition R easily reduced), In addition, the impact resistance of the obtained molded product can be enhanced.
[0051]
　"The melting point (Tm) is not substantially measured" means that the endothermic peak based on crystal melting in the second heating (from room temperature to 330 ° C.) in the above-mentioned measurement of the melting point using a differential scanning calorimeter (DSC). Is virtually unobserved. The fact that the endothermic peak is not substantially observed means that the heat of fusion (ΔH) of the polyamide resin (B) measured by differential scanning calorimetry (DSC) is 5 J / g or less.
[0052]
　That is, the heat of fusion (ΔH) of the polyamide resin (B) measured by differential scanning calorimetry (DSC) is preferably 5 J / g or less, and more preferably 0 J / g. When the heat of fusion (ΔH) of the polyamide resin (B) is 5 J / g or less, the crystallinity is appropriately low, so that the compatibility with the polyamide resin (A) is excellent and the appearance of the molded product of the polyamide resin composition is excellent. Is preferable in that it is excellent. The polyamide resin (B) preferably exhibits amorphousness. The heat of fusion (ΔH) can be measured by the same method as described above.
[0053]
　The polyamide resin (B) contains a component unit (b1) derived from a dicarboxylic acid and a component unit (b2) derived from a diamine.
[0054]
　[Component unit derived from dicarboxylic acid (b1)] The
　component unit derived from dicarboxylic acid (b1) preferably contains at least a component unit derived from isophthalic acid. The component unit derived from isophthalic acid can lower the crystallinity of the polyamide resin (B).
[0055]
　The content of the component unit derived from isophthalic acid is preferably 40 mol% or more, more preferably 50 mol% or more, based on the total amount of the component unit (b1) derived from dicarboxylic acid. When the content of the component unit derived from isophthalic acid is 40 mol% or more, it is easy to reduce the irradiation energy of the laser beam required for laser welding on the obtained molded product.
[0056]
　The component unit derived from dicarboxylic acid (b1) may further contain a component unit derived from dicarboxylic acid other than the component unit derived from isophthalic acid as long as the effect of the present invention is not impaired. Examples of other dicarboxylic acids include aromatic dicarboxylic acids other than isophthalic acids such as terephthalic acid, 2-methylterephthalic acid and naphthalenedicarboxylic acids; aliphatic dicarboxylic acids; and alicyclic dicarboxylic acids. The aliphatic dicarboxylic acid and the alicyclic dicarboxylic acid can be the same as the above-mentioned aliphatic dicarboxylic acid and the alicyclic dicarboxylic acid, respectively. Among them, aromatic dicarboxylic acids other than isophthalic acid are preferable, and terephthalic acid is more preferable.
[0057]
　The molar ratio of the component unit derived from isophthalic acid to the component unit derived from an aromatic dicarboxylic acid (preferably terephthalic acid) other than isophthalic acid in the component unit derived from dicarboxylic acid (b1) is the component derived from isophthalic acid. Unit / component unit derived from aromatic dicarboxylic acid (preferably terephthalic acid) other than isophthalic acid = 55/45 to 100/0 (molar ratio), preferably 60/40 to 90/10 (molar ratio) Is more preferable. When the amount of the component unit derived from isophthalic acid is a certain amount or more, the polyamide resin (B) tends to be amorphous, and the irradiation energy of laser light required for laser welding in the obtained molded product is likely to be reduced. When the amount of the component unit derived from isophthalic acid is less than a certain level, the heat resistance and mechanical strength of the obtained molded product are not easily impaired.
[0058]
　[Component unit derived from diamine (b2)] The
　component unit derived from diamine (b2) preferably contains a component unit derived from an aliphatic diamine having 4 to 15 carbon atoms.
[0059]
　The aliphatic diamine having 4 to 15 carbon atoms is the same as the above-mentioned aliphatic diamine having 4 to 15 carbon atoms, and is preferably 1,6-hexanediamine.
[0060]
　The content of the component unit derived from the aliphatic diamine having 4 to 15 carbon atoms is preferably 50 mol% or more, preferably 60 mol% or more, based on the total amount of the component units (b2) derived from the diamine. More preferably.
[0061]
　The component unit derived from diamine (b2) may further contain a component unit derived from a diamine other than the component unit derived from an aliphatic diamine having 4 to 15 carbon atoms as long as the effect of the present invention is not impaired. Good. Examples of other diamines include alicyclic diamines and aromatic diamines. The alicyclic diamine and the aromatic diamine can be the same as the alicyclic diamine and the aromatic diamine described above, respectively. The content of the other diamine component unit is 50 mol% or less, preferably 40 mol% or less.
[0062]
　Specific examples of the polyamide resin (B) include isophthalic acid / terephthalic acid / 1,6-hexanediamine / bis (3-methyl-4-aminocyclohexyl) methane polycondensate, isophthalic acid / bis (3-methyl-). 4-Aminocyclohexyl) methane / ω-laurolactum polycondensate, isophthalic acid / terephthalic acid / 1,6-hexanediamine polycondensate, isophthalic acid / 2,2,4-trimethyl-1,6-hexanediamine Polycondensate of / 2,4,4-trimethyl-1,6-hexanediamine, isophthalic acid / terephthalic acid / 2,2,4-trimethyl-1,6-hexanediamine / 2,4,4-trimethyl-1 , 6-Hexanediamine polycondensate, isophthalic acid / bis (3-methyl-4-aminocyclohexyl) methane / ω-laurolactum polycondensate, isophthalic acid / terephthalic acid / other diamine component polycondensate, etc. Is included. Of these, a polycondensate of isophthalic acid / terephthalic acid / 1,6-hexanediamine is preferable. Only one type of polyamide resin (B) may be contained, or two or more types may be contained.
[0063]
　The ultimate viscosity [η] of the polyamide resin (B) measured in 96.5% sulfuric acid at a temperature of 25 ° C. is preferably 0.6 to 1.6 dl / g, preferably 0.65 to 1.2 dl. It is more preferably / g. The ultimate viscosity [η] of the polyamide resin (B) can be measured by the same method as the above-mentioned ultimate viscosity [η] of the polyamide resin (A).
[0064]
　The polyamide resin (B) can be produced in the same manner as the above-mentioned polyamide resin (A).
[0065]
　The content of the polyamide resin (B) is 0 to 45 when the total of the polyamide resin (A), the polyamide resin (B), the light-transmitting dye (C) and the fibrous filler (D) is 100 parts by mass. The amount is preferably 0.1 to 45 parts by mass, and may be 5 to 35 parts by mass. When the content of the polyamide resin (B) is 0.1 parts by mass or more, the obtained molded product is easily laser welded even with a small irradiation energy, and when it is 45 parts by mass or less, the mechanical strength and heat resistance of the molded product The property (deflection under load) is not significantly impaired.
[0066]
　The content of the polyamide resin (B) is preferably 0 to 60 parts by mass, preferably 5 to 50 parts by mass, based on 100 parts by mass of the total of the polyamide resin (A) and the polyamide resin (B). More preferably, it is 10 to 40 parts by mass. When the content of the polyamide resin (B) with respect to a total of 100 parts by mass of the polyamide resin (A) and the polyamide resin (B) is 5 parts by mass or more, the irradiation energy of the laser beam required for welding is applied to the obtained molded product. It is easy to reduce, and when it is 50 parts by mass or less, it is easy to impart sufficient heat resistance and rigidity (deflection under load) to the molded product.
[0067]
　1-3. Light-transmitting dye (C) The
　light-transmitting dye (C) is a component for coloring a polyamide resin composition without lowering the transmittance for laser light. That is, the light-transmitting dye (C) is a dye having transparency to laser light, and specifically, a dye having no maximum absorption wavelength in the wavelength range of 800 to 1064 nm.
[0068]
　The light-transmitting dye (C) is preferably a black dye that satisfies the characteristics described later. Examples of such black pigments include naphthalocyanines, aniline blacks, phthalocyanines, porphyrins, perylenes, quaterylenes, azo dyes, anthraquinones, square acid derivatives, and immonium dyes.
[0069]
　Examples of commercially available light-transmitting dyes (C) include eBind ACW-9871, e-BIND LTW-8731H, and e-BIND LTD LTW-8701H, which are colorants manufactured by Orient Chemical Industries, Ltd. Further, a black pigment may be used by mixing two or more kinds of chromatic pigments.
[0070]
　The content of the light-transmitting dye (C) may be set so that the light transmittance of the polyamide resin composition at a wavelength of 940 nm is in the range described later. Specifically, the content of the light-transmitting dye (C) is 100 parts by mass of the total of the polyamide resin (A), the polyamide resin (B), the light-transmitting dye (C) and the fibrous filler (D). When it is, it is preferably 0.1 to 5 parts by mass. When the content of the light-transmitting dye (C) is 0.1 parts by mass or more, it is easy to sufficiently color, so that it is easy to enhance the design, and when it is 5 parts by mass or less, the transmittance of the laser light is remarkably lowered. It is possible to more reliably suppress the remarkable decrease in welding strength due to this, and the deterioration of continuous productivity during kneading and molding due to the decomposition of pigment components. From the above viewpoint, the content of the light-transmitting dye (C) is 100 parts by mass of the total of the polyamide resin (A), the polyamide resin (B), the light-transmitting dye (C) and the fibrous filler (D). When it is, it is preferably 0.1 to 4 parts by mass, more preferably 0.1 to 3 parts by mass, and further preferably 0.25 to 2.5 parts by mass.
[0071]
　The light-transmitting dye (C) may contain only one type, or may contain two or more types. When two or more types are included, the total amount is preferably in the above range.
[0072]
　1-4. Fibrous Filler (D)
　Examples of fibrous filler (D) include glass fiber, wallastnite, potassium titanate whiskers, calcium carbonate whiskers, aluminum borate whiskers, magnesium sulfate whiskers, zinc oxide whiskers, and milled fibers. And cut fiber etc. are included. Of these, one type may be used alone, or two or more types may be used in combination. Among them, wallastnite, glass fiber, and potassium titanate whiskers are preferable, and wallastnite or glass fiber is more preferable, because it is easy to increase the mechanical strength of the molded product.
[0073]
　The average fiber length of the fibrous filler (D) is preferably 1 μm to 20 mm, preferably 5 μm to 10 mm, from the viewpoint of the moldability of the polyamide resin composition and the mechanical strength and heat resistance of the obtained molded product. It is more preferably present, and further preferably 10 μm to 5 mm. The aspect ratio of the fibrous filler (D) is preferably 5 to 2000, more preferably 30 to 600.
[0074]
　The average fiber length and average fiber diameter of the fibrous filler (D) can be measured by the following methods.
　1) The polyamide resin composition is dissolved in a hexafluoroisopropanol / chloroform solution (0.1 / 0.9% by volume), and then the filtered product obtained by filtration is collected.
　2) The filtrate obtained in 1) above is dispersed in water, and the fiber length (Li) and fiber diameter (di) of each of 300 arbitrary fibers are measured with an optical microscope (magnification: 50 times). Let qi be the number of fibers having a fiber length of Li, calculate the weight average length (Lw) based on the following equation, and use this as the average fiber length of the fibrous filler (D).
　Weight average length (Lw) = (Σqi × Li 2 ) / (Σqi × Li)
　Similarly, let ri be the number of fibers having a fiber diameter of Di, and calculate the weight average diameter (Dw) based on the following equation. Let this be the average fiber diameter of the fibrous filler (D).
　Weight average diameter (Dw) = (Σri × Di 2 ) / (Σri × Di)
[0075]
　The fibrous filler (D) may be surface-treated. When the surface treatment is applied, the adhesiveness with the polyamide resin (A), which is a matrix resin, tends to increase. Examples of surface treatment agents include coupling agents such as silane-based coupling agents, titanium-based coupling agents, and aluminate-based coupling agents; sizing agents and the like. Examples of commonly used coupling agents include aminosilane, epoxysilane, methyltrimethoxysilane, methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, vinyltriacetoxysilane and vinyltrimethoxysilane. .. Further, examples of the focusing agent preferably used include an epoxy compound, a urethane compound, a carboxylic acid compound, a urethane / maleic acid-modified compound and a urethane / amine-modified compound. The fibrous filler (D) may be treated with one kind of surface treatment agent, or may be treated with two or more kinds of surface treatment agents. In particular, when treated with the coupling agent and the sizing agent, the adhesiveness between the fibrous filler (D) and the polyamide resin (A) tends to increase, and the mechanical properties of the obtained molded product tend to increase.
[0076]
　The content of the fibrous filler (D) is 10 when the total of the polyamide resin (A), the polyamide resin (B), the light-transmitting dye (C) and the fibrous filler (D) is 100 parts by mass. It is preferably about 55 parts by mass. When the content of the fibrous filler (D) is 10 parts by mass or more, it is easy to impart high mechanical strength and heat resistance to the molded product. When the content of the fibrous filler (D) is 55 parts by mass or less, the transmission of the laser beam of the molded product is unlikely to be impaired, and the resulting decrease in welding strength and excessive increase in viscosity during molding are unlikely to occur. .. The content of the fibrous filler (D) is 10 when the total of the polyamide resin (A), the polyamide resin (B), the light-transmitting dye (C) and the fibrous filler (D) is 100 parts by mass. It is preferably up to 50 parts by mass, more preferably 25 to 45 parts by mass, and even more preferably 30 to 40 parts by mass.
[0077]
　1-5. Other Component (E)
　The polyamide resin composition of the present invention may be other than the polyamide resin (A), the polyamide resin (B), the light-transmitting dye (C), and the fibrous filler (D), if necessary. The component (E) may be further contained. Examples of other components include nucleating agents, elastomers (rubbers), flame retardants (bromine-based, chlorine-based, phosphorus-based, antimony-based and inorganic-based, etc.), fluidity improvers, antistatic agents, mold release agents, oxidation. Inhibitors (phenols, amines, sulfur and phosphorus, etc.), heat-resistant stabilizers (lactone compounds, vitamin Es, hydroquinones, copper halides and iodine compounds, etc.), light stabilizers (benzotriazoles, triazines, etc.) , Benzophenones, benzoates, hindered amines and ogizanilides, etc.), other polymers (polyolefins, ethylene / propylene copolymers, ethylene / 1-butene copolymers and other olefin copolymers, propylene / 1-butene, etc. Olefin copolymers such as copolymers, polystyrene, polyamide, polycarbonate, polyacetal, polysulphon, polyphenylene oxide, fluororesin, silicone resin and LCP) and the like are included. The total content of the other components is not particularly limited, but is preferably 30% by mass or less, and more preferably 10% by mass or less, based on the total mass of the polyamide resin composition.
[0078]
　1-5-1. The nucleating agent The nucleating agent
　may be a plate-like, powder-like or granular filler as long as it promotes the crystallization of the polyamide resin (A) or the polyamide resin (B).
[0079]
　Examples of nuclear agents include silicates such as talc, zeolite, sericite, mica, kaolin, clay, pyrophyllite and bentonite, metal compounds such as magnesium oxide, alumina, zirconium oxide and iron oxide, calcium carbonate and magnesium carbonate. , Carbonate such as dolomite, calcium sulfate, sulfate such as barium sulfate, glass beads, ceramic beads, boron nitride, calcium phosphate, calcium hydroxide, magnesium hydroxide, hydroxide such as aluminum hydroxide, glass flakes , Glass powder, glass balloons, carbon black and silica, non-fibrous fillers such as graphite, and smectite clay minerals such as montmorillonite, biderite, nontronite, saponite, hectolite, soconite, vermiculite, halloysite, kaolinite, kenyite , Various clay minerals such as zirconium phosphate and titanium phosphate, layered silicates typified by swelling mica such as Li-type fluorine teniolite, Na-type fluorine teniolite, Na-type tetrasilicon fluorine mica, and Li-type tetrasilicon fluorine mica. .. The layered silicate may be a layered silicate in which exchangeable cations existing between layers are exchanged with organic onium ions, and the organic onium ions include ammonium ion, phosphonium ion, sulfonium ion and the like. These nucleating agents may be used alone or in combination of two or more. Among them, plate-like fillers such as talc, mica, kaolin, clay, glass flakes, carbon black, graphite and montmorillonite are preferable, and talc, mica and glass flakes are more preferable.
[0080]
　The nucleating agent may be further treated with a silane-based or titanate-based coupling agent or other surface treatment agent. Among them, the nucleating agent treated with an epoxysilane or aminosilane-based coupling agent is easy to disperse well in the resin component and can promote the crystallization of the polyamide resin (A) and the polyamide resin (B). Good mechanical strength can be imparted to the molded product.
[0081]
　The average particle size of the nucleating agent is preferably 0.1 to 30 μm. When the average particle size of the nucleating agent is 0.1 μm or more, the spherulites of the obtained molded body are easily refined, and when the average particle size is 30 μm or less, the appearance of the surface of the molded body is not easily deteriorated. The average particle size of the nucleating agent is more preferably 0.5 to 25 μm, and even more preferably 1.0 to 23 μm. The average particle size of the nucleating agent is an arithmetic average size obtained by measuring by a laser diffraction / scattering method, and is a volume average particle size (MV).
[0082]
　The content of the nucleating agent is preferably 0.01 to 10% by mass with respect to the total mass of the polyamide resin composition. When the content of the nucleating agent is 0.01% by mass or more, the crystallization of the polyamide resin can be sufficiently promoted, so that the spherulite of the obtained molded product can be easily refined, and when it is 10% by mass or less, molding The property and surface appearance are not easily impaired. The content of the nucleating agent is preferably 0.01 to 5% by mass, more preferably 0.1 to 2% by mass, based on the total mass of the polyamide resin composition.
[0083]
　It is preferable that the polyamide resin composition of the present invention does not substantially contain a light-absorbing dye. The term "substantially free" means, for example, 0.0001% by mass or less of the polyamide resin composition.
[0084]
　1-6. Physical properties
　(corrected heat of fusion ([Delta] H R ))
　of the polyamide resin composition of the present invention, the correction heat of fusion as measured by differential scanning calorimetry (DSC) ([Delta] H R ) is preferably 10 ~ 70J / g. Correction heat of fusion of the polyamide resin composition ([Delta] H R If) is 10J / g or more, tends sufficiently increase the heat resistance of the molded article, is not more than 70 J / g, most of the energy of the laser light crystallization unit Since it is not consumed in the melting of the resin and it is easy to form a large molten portion, it is easy to increase the welding strength. Correction heat of fusion of the polyamide resin composition ([Delta] H R ), from the viewpoint of easier to enhance the weld strength, and more preferably 10 ~ 53J / g.
[0085]
　Correction heat of fusion ([Delta] H R A), heat of fusion and ([Delta] H) of the polyamide resin composition, a value obtained by dividing the ratio of the total weight of components other than the fibrous filler (D) to the total weight of the polyamide resin composition is there. The heat of fusion (ΔH) of the polyamide resin composition can be measured by the same method as the heat of fusion (ΔH) of the polyamide resins (A) and (B).
[0086]
　Correction heat of fusion of the polyamide resin composition ([Delta] H R ) can be adjusted composition and the polyamide resin (A), such as by the content ratio of the polyamide resin (A) and the polyamide resin (B). Correction heat of fusion ([Delta] H R method to lower the),
[0087]
　(Transmittance of Laser Light)
　The transmittance of laser light having a wavelength of 940 nm of the polyamide resin composition of the present invention is preferably 15% or more, preferably 36% or more when the thickness of the molded product is 1.6 mm. More preferably, it is more preferably 45% or more. When the thickness of the molded product of the polyamide resin composition of the present invention is 3.2 mm, the transmittance of the laser light having a wavelength of 940 nm is preferably 7.2% or more, and is preferably 10% or more. Is more preferable, and 12% or more is further preferable. The upper limit of the transmittance of the laser light having a wavelength of 940 nm is not particularly limited, but may be, for example, 70% or 60%. The transmittance of the laser light of the polyamide resin composition can be measured by comparing the laser light intensity when the sample is transmitted and when the sample is not transmitted by the power meter F300-SH manufactured by Ophir.
[0088]
　The transmittance of laser light having a wavelength of 940 nm can be adjusted by adjusting the composition of the polyamide resin (A) and the type and content of the light transmitting dye (C). In order to increase the transmittance of laser light having a wavelength of 940 nm, it is preferable that the component constituting the polyamide resin (A) contains a component having not too high crystallinity, and the content of the light transmitting dye (C) is high. It is preferable to reduce the amount.
[0089]
　As described above, the polyimide resin composition of the present invention has high transparency to laser light even though it contains the fibrous filler (D). Therefore, the polyamide resin composition of the present invention can be preferably used as a light-transmitting resin composition for laser welding.
[0090]
　2. 2. Method for Producing Polyamide Resin Composition The method for producing the polyamide resin composition of the
　present invention is not particularly limited, but at least the above-mentioned ratios of the polyamide resin (A), the polyamide resin (B), the light-transmitting dye (C) and the fiber The state filler (D) can be produced through a step of melt-kneading with a uniaxial extruder, a multi-screw extruder, a kneader, a Banbury mixer, or the like, and a step of granulating or crushing the melt-kneaded product. If necessary, before the melt-kneading step, a step of mixing by a known method, for example, a method of mixing with a Henschel mixer, a V blender, a ribbon blender, a tumbler blender, or the like may be carried out.
[0091]
　Above all, a method of melt-kneading using a single-screw or twin-screw extruder having equipment capable of devolatile from the vent port is preferable. The polyamide resin (A), polyamide resin (B), light-transmitting dye (C), fibrous filler (D) and other components (E) to be blended as needed are collectively supplied to the extruder. Alternatively, the polyamide resin (A) may be sequentially supplied with other compounding components. The fibrous filler (D) such as glass fiber is preferably supplied from the middle of the extruder in order to prevent crushing during kneading. Further, two or more kinds of the above-mentioned components (A) to (D) may be mixed and kneaded in advance. For example, niglosin as the light-transmitting dye (C) may be prepared in advance as a masterbatch using a thermoplastic resin, and this may be melt-mixed and extruded with the remaining compounding components to obtain a predetermined compounding ratio.
[0092]
　The thermoplastic resin used in the masterbatch is preferably a polyamide resin. The polyamide resin used in the master batch may be a polyamide resin (A), or may be a polyamide resin other than the polyamide resin (A), such as polyamide 6 or polyamide 66. For example, a light-transmitting dye (C) master-batched with polyamide 66 can be used.
[0093]
　3. 3. Molded article
　The molded article of the present invention can be obtained by molding the polyamide resin composition of the present invention.
[0094]
　The molding method is not particularly limited, and known molding methods, that is, molding methods such as injection molding, hollow molding, extrusion molding, and press molding can be applied. Above all, injection molding is preferable from the viewpoint of good fluidity. In the injection molding method, it is preferable to adjust the resin temperature to 250 to 300 ° C.
[0095]
　The molded product of the polyamide resin composition of the present invention has high transparency to laser light even though it contains the fibrous filler (D). Therefore, the molded product of the polyamide resin composition of the present invention can be preferably used as a light-transmitting resin member that transmits laser light in the laser welding method.
[0096]
　4. Method for Producing Laser Welder In the
　present invention, a molded product of the polyamide resin composition of the present invention (first molded product, a light-transmitting resin member) and a molded product of a light-absorbing resin composition (second molded product, light). An absorbent resin member) can be irradiated with laser light through the first molded body (light-transmitting resin member) and welded to produce a laser-welded body. Thereby, the first molded body (light-transmitting resin member) and the second molded body (light-absorbing resin member) can be firmly welded without using an adhesive.
[0097]
　First, the light-absorbing resin composition constituting the second molded product, which is a light-absorbing resin member, will be described.
[0098]
　4-1. Light-absorbing resin composition The
　light-absorbing resin composition contains a thermoplastic resin and a light-absorbing dye.
[0099]
　4-1-1. Thermoplastic resin The
　thermoplastic resin is not particularly limited, but is preferably a polyamide resin from the viewpoint of easily obtaining good welding strength with the molded body of the polyamide resin composition of the present invention.
[0100]
　The melting point (Tm) measured by a differential scanning calorimeter (DSC) of the polyamide resin is preferably 290 to 340 ° C. The glass transition temperature (Tg) measured by a differential scanning calorimeter (DSC) of the polyamide resin is preferably 75 to 150 ° C. The melting point (Tm) and the glass transition temperature (Tg) of the polyamide resin can be measured by the same method as described above. A light-absorbing resin composition containing a polyamide resin having such a melting point (Tm) and a glass transition temperature (Tg) not only has high mechanical strength and heat resistance, but is also included in the above-mentioned polyamide resin composition. Since the affinity with the polyamide resin (A) is good, it is easy to increase the welding strength of the above-mentioned polyamide resin composition with the molded body (first molded body).
[0101]
　The polyamide resin is not particularly limited as long as the melting point (Tm) and the glass transition temperature (Tg) satisfy the above ranges. Examples of polyamide resins include component units derived from diamines and component units derived from aliphatic dicarboxylic acids having 8 or less carbon atoms; component units derived from aromatic dicarboxylic acids and aliphatic diamines. It also includes those containing the derived component units. Of these, a polyamide resin containing a component unit derived from an aromatic dicarboxylic acid and a component unit derived from an aliphatic diamine is preferable. As such a polyamide resin, the same one as the above-mentioned polyamide resin (A) can be used. From the viewpoint of obtaining good welding strength, it is more preferable that the polyamide resin (A) contained in the polyamide resin composition of the present invention and the polyamide resin contained in the light-absorbing resin composition are the same.
[0102]
　The resin component contained in the light-absorbing resin composition and the resin component contained in the polyamide resin composition of the present invention are preferably 90% by mass or more in common.
[0103]
　4-1-2. Light-absorbing dye The
　light-absorbing dye is a dye having an absorption wavelength in the wavelength range of the laser light to be irradiated, that is, in the wavelength range of 800 to 1064 nm. Such a light-absorbing dye absorbs laser light and generates heat to melt the thermoplastic resin. By the heat, the resin component contained in the first molded product is also melted, so that it can be welded.
[0104]
　The light-absorbing dye may be an inorganic pigment or an organic pigment. Examples of inorganic pigments are black pigments such as carbon black (eg, acetylene black, lamp black, thermal black, furnace black, channel black, ketjen black); red pigments such as iron oxide red; orange such as molybdate orange. Pigments: Includes white pigments such as titanium oxide. Examples of organic pigments include yellow pigments, orange pigments, red pigments, blue pigments, green pigments and the like. Of these, inorganic pigments are generally preferable because they have a strong hiding power, and black pigments are more preferable.
[0105]
　The light-absorbing dye is preferably added as a masterbatch during the production of the light-absorbing resin composition from the viewpoint of improving the dispersibility. Examples of the carbon black masterbatch include PA-0896A (masterbatch having a carbon black content of 50% by mass) manufactured by Nikko Bics Co., Ltd.
[0106]
　One type of light-absorbing dye may be used, or two or more types may be used in combination. The content of the light-absorbing dye is preferably 0.01 to 1 part by mass with respect to 100 parts by mass of the resin component.
[0107]
　4-1-3. Other components The
　light-absorbing resin composition may further contain a fibrous filler, a nucleating agent, and the like, if necessary.
[0108]
　As the fibrous filler, the same fibrous filler as the above-mentioned fibrous filler (D) can be used. Above all, the fibrous filler is preferably glass fiber. The average fiber length and aspect ratio of the fibrous filler can be the same as described above. As the nucleating agent, the same nucleating agent (E) as described above can be used.
[0109]
　4-2. Method for Producing Laser Welded Body
　Next, the method for manufacturing the laser welded body of the present invention will be described.
[0110]
　The method for producing the laser welded product of the present invention is as follows: 1) a step of obtaining a molded product (first molded product) of the polyamide resin composition of the present invention, and 2) a molded product of the above-mentioned photoabsorbable resin composition (second molded product). The step of obtaining a molded body) and 3) the first molded body and the second molded body are superposed, and laser light is irradiated through the first molded body to weld the first molded body and the second molded body. Including the step of making.
[0111]
　About Steps 1) and 2) In the step
　1), the polyamide resin composition of the present invention is molded to obtain a molded product (first molded product). In the step 2), the above-mentioned light-absorbing resin composition may be molded to obtain a molded product (second molded product), or a commercially available product may be used. The molding method is 3. It is the same as the molding method in the molded body.
[0112]
　The shapes of the first molded body and the second molded body are not particularly limited, but since the molded bodies are used by joining them by laser welding, they usually have at least a surface (plane or curved surface) capable of surface contact. In laser welding, the laser light transmitted through the first molded body, which is a light-transmitting resin member, is absorbed by the second molded body, which is a light-absorbing resin member, and melts, and both members are welded. Although the first molded product obtained by molding the polyamide resin composition of the present invention contains the fibrous filler (D), it has high transparency to laser light. Therefore, the transparent resin in the laser welding method. It can be preferably used as a member.
[0113]
　The thickness of the first molded product (thickness in the laser transmission direction in the portion through which the laser light is transmitted) can be appropriately set in consideration of the application, the composition of the polyamide resin composition, and the like, but is preferably 5 mm or less, for example. It is 4 mm or less.
[0114]
　Regarding
　the step 3), the first molded body and the second molded body are superposed, and laser light is irradiated through the first molded body to laser weld the first molded body and the second molded body.
[0115]
　Specifically, the welded portions of the first molded body and the second molded body are brought into mutual contact with each other. At this time, it is preferable that the welded portions of the first molded body and the second molded body are in surface contact with each other. The surface contact may be a contact between flat surfaces, a contact between curved surfaces, or a contact between a flat surface and a curved surface.
[0116]
　Next, the laser beam is irradiated through the first molded body which is a light transmitting resin member. Irradiation of the laser light is preferably performed from an angle of 85 to 95 ° with respect to the welded surface from the viewpoint of making it easy for the laser light to reach the welded surface efficiently. Further, if necessary, a lens system may be used to focus the laser beam on the interface between the first molded body and the second molded body. The focused beam passes through the first molded body, is absorbed near the surface of the second molded body, generates heat, and melts. Next, the heat is transferred to the first molded body by heat conduction and melted, and a molten pool is formed at the interface between the two. This molten pool is cooled and solidified to become a welded portion (joint portion).
[0117]
　The laser light source used can be selected according to the light of the light absorbing dye. For example, a laser light source having a wavelength of 800 to 1064 nm is preferable, and for example, a semiconductor laser can be used.
[0118]
　The laser welded body obtained by laser welding the first molded body and the second molded body in this way has a high welding strength (bonding strength). The laser welded body in the present invention includes not only finished products and parts, but also members forming a part thereof.
[0119]
　(Laser welded body) The
　obtained laser welded body has good mechanical strength, high welding strength, and less damage to the resin due to laser light irradiation. Therefore, the obtained laser welded body can be applied to various uses, for example, various storage containers, electrical / electronic equipment parts, office automation (OA) equipment parts, home appliance parts, mechanical mechanism parts, vehicle mechanism parts, and the like. .. In particular, food containers, chemical containers, oil and fat product containers, hollow parts for vehicles (various tanks, intake manifold parts, temperature control valve parts, thermostat cases, camera housings, etc.), electrical parts for vehicles (various control units, ignitions, etc.) (Coil parts, etc.) It can be suitably used for motor parts, various sensor parts, connector parts, switch parts, breaker parts, relay parts, coil parts, transformer parts, lamp parts, and the like.
Example
[0120]
　Hereinafter, the present invention will be described with reference to Examples. The scope of the present invention is not construed as limiting by the examples.
[0121]
　1. 1. Material Preparation
　(1) Polyamide Resin (A)
　
　2,800 g (24.1 mol) of 1,6-hexanediamine, 2774 g (16.7 mol) of terephthalic acid, 1196 g of isophthalic acid (1196 g) 7.2 mol), 36.6 g (0.30 mol) of benzoic acid, 5.7 g of sodium hypophosphate monohydrate and 545 g of distilled water were placed in an autoclave having an content of 13.6 L and replaced with nitrogen. Stirring was started at 190 ° C. and the internal temperature was raised to 250 ° C. over 3 hours. At this time, the internal pressure of the autoclave was increased to 3.03 MPa. After continuing the reaction for 1 hour as it was, the low-order condensate was extracted by releasing it into the atmosphere from a spray nozzle installed in the lower part of the autoclave. Then, the low-order condensate was cooled to room temperature, the low-order condensate was pulverized with a pulverizer to a particle size of 1.5 mm or less, and dried at 110 ° C. for 24 hours. The water content of the obtained low-order condensate was 4100 ppm, and the ultimate viscosity [η] was 0.15 dl / g.
　Next, this low-order condensate was placed in a shelf-stage solid-state polymerization apparatus, and after nitrogen substitution, the temperature was raised to 180 ° C. over about 1 hour and 30 minutes. Then, the reaction was carried out for 1 hour and 30 minutes, and the temperature was lowered to room temperature. The ultimate viscosity [η] of the obtained prepolymer was 0.20 dl / g.
　Then, the obtained prepolymer was melt-polymerized by a twin-screw extruder having a screw diameter of 30 mm and L / D = 36 at a barrel set temperature of 330 ° C., a screw rotation speed of 200 rpm, and a resin supply rate of 6 kg / h. , Polyamide resin (A-1) was obtained.
　The obtained polyamide resin (A-1) had an ultimate viscosity of 1.0 dl / g, a melting point (Tm) of 330 ° C., a glass transition temperature (Tg) of 125 ° C., and a terminal amino group amount of 30 mmol / kg.
[0122]
　
　1,6-Hexamethylenediamine 2800 g (24.1 mol), Terephthalic Acid 2176 g (13.1 mol), Adipic Acid 1578 g (10.8 mol), Benzoic Acid 36.6 g (0.30 mol), 5.7 g of sodium hypophosphate monohydrate and 554 g of distilled water were placed in an autoclave having a content of 13.6 L and substituted with nitrogen. Stirring was started at 190 ° C. and the internal temperature was raised to 250 ° C. over 3 hours. At this time, the internal pressure of the autoclave was increased to 3.01 MPa. After continuing the reaction for 1 hour as it was, the low condensate was extracted by releasing it into the atmosphere from a spray nozzle installed in the lower part of the autoclave. Then, this low condensate was cooled to room temperature, pulverized with a pulverizer to a particle size of 1.5 mm or less, and dried at 110 ° C. for 24 hours. The water content of the obtained low condensate was 3600 ppm, and the ultimate viscosity [η] was 0.14 dl / g.
　Next, this low condensate was placed in a shelf-type solid phase polymerization apparatus, and after nitrogen substitution, the temperature was raised to 220 ° C. over about 1 hour and 30 minutes. Then, the reaction was carried out for 1 hour, and the temperature was lowered to room temperature. The ultimate viscosity [η] of the obtained prepolymer was 0.48 dl / g.
　Then, the obtained prepolymer was melt-polymerized by a twin-screw extruder having a screw diameter of 30 mm and L / D = 36 at a barrel set temperature of 330 ° C., a screw rotation speed of 200 rpm, and a resin supply rate of 6 kg / h. A polyamide resin (A-2) was obtained.
　The obtained polyamide resin (A-2) has an ultimate viscosity [η] of 1.0 dl / g, a melting point (Tm) of 310 ° C., a glass transition temperature (Tg) of 85 ° C., and a terminal amino group amount of 45 mmol / kg. there were.
[0123]
　 The
　raw materials are 1,6-hexanediamine 2905 g (25.0 mol), terephthalic acid 2475 g (14.9 mol), adipic acid 1461 g (10.0 mol), and benzoic acid. Polyamide resin (A-3) was obtained in the same manner as in the preparation of polyamide resin (A-1) except that it was changed to 73.2 g (0.60 mol) and 5.7 g of sodium hypophosphate monohydrate. It was.
　The obtained polyamide resin (A-3) has an ultimate viscosity [η] of 0.8 dl / g, a terminal amino group amount of 110 mmol / kg, a melting point (Tm) of 320 ° C., and a glass transition temperature (Tg) of 95 ° C. there were.
[0124]
　
　1,6-hexanediamine 1312 g (11.3 mol), 2-methyl-1,5-pentanediamine 1312 g (11.3 mol), terephthalic acid 3655 g (22.0 mol) mol), the following sodium phosphite 5.5 g (5.2 × 10 as a catalyst -2 mol), and deionized water 640ml were charged into a 1 liter reactor. after nitrogen substitution, 250 ° C., 35 kg / cm 2 of The reaction was carried out under the conditions for 1 hour. The molar ratio of 1,6-hexanediamine to 2-methyl-1,5-pentanediamine was 50:50. After 1 hour, the reaction product produced in the reactor was withdrawn into a receiver connected to the reactor and the pressure was set to be about 10 kg / cm 2 lower, and the ultimate viscosity [η] was 0.15 dl. A prepolymer of / g was obtained.
　Next, the obtained prepolymer was dried and then melt-polymerized at a cylinder set temperature of 330 ° C. using a twin-screw extruder to obtain a polyamide resin (A-4).
　The obtained polyamide resin (A-4) has an ultimate viscosity [η] of 1.0 dl / g, a melting point (Tm) of 300 ° C., a glass transition temperature (Tg) of 140 ° C., and a terminal amino group amount of 45 mmol / kg. there were.
[0125]
　 A
　mixture of 1,9-nonandiamine and 2-methyl-1,8-octanediamine [1,9-nonandiamine: 2-methyl-1,8-octanediamine = 80: 20 (molar ratio)] 4385 g (27.7 mol), 4537.7 g of terephthalic acid (27.3 mol), 9.12 g of sodium hypophosphate monohydrate (0.1 mass with respect to the total mass of the raw material) %) And 2.5 liters of distilled water were placed in an autoclave having an internal volume of 20 L and substituted with nitrogen. The mixture was stirred at 100 ° C. for 30 minutes, and the temperature inside the autoclave was raised to 220 ° C. over 2 hours. At this time, the pressure inside the autoclave was increased to 2 MPa. After continuing the reaction for 2 hours as it was, the temperature was raised to 230 ° C., then the temperature was maintained at 230 ° C. for 2 hours, water vapor was gradually removed, and the reaction was carried out while maintaining the pressure at 2 MPa. Next, the pressure was lowered to 1 MPa over 30 minutes, and the reaction was further carried out for 1 hour to obtain a prepolymer having an ultimate viscosity [η] of 0.15 dl / g.
　The obtained prepolymer was dried at 100 ° C. under reduced pressure for 12 hours and then pulverized to a particle size of 2 mm or less. The pulverized prepolymer was solid-phase polymerized at 230 ° C. and 13 Pa (0.1 mmHg) for 10 hours to obtain a polyamide resin (A-5).
　The obtained polyamide resin (A-5) has an ultimate viscosity [η] of 1.2 dl / g, a melting point (Tm) of 300 ° C., a glass transition temperature (Tg) of 120 ° C., and a terminal amino group amount of 80 mmol / kg. there were.
[0126]
　(2) Polyamide resin (B)
　
　1,6-hexanediamine 2800 g (24.1 mol), terephthalic acid 1390 g (8.4 mol), isophthalic acid 2581 g (15.5 mol) Mol), 109.5 g (0.9 mol) of benzoic acid, 5.7 g of sodium hypophosphate monohydrate and 545 g of distilled water were placed in an autoclave having a content of 13.6 L and substituted with nitrogen. Stirring was started at 190 ° C. and the internal temperature was raised to 250 ° C. over 3 hours. At this time, the internal pressure of the autoclave was increased to 3.02 MPa. After continuing the reaction for 1 hour as it was, the low-order condensate was extracted by releasing it into the atmosphere from a spray nozzle installed in the lower part of the autoclave. Then, the low-order condensate was cooled to room temperature, pulverized with a pulverizer to a particle size of 1.5 mm or less, and dried at 110 ° C. for 24 hours. The water content of the obtained low-order condensate was 3000 ppm, and the ultimate viscosity [η] was 0.14 dl / g.
　Next, this low-order condensate is melt-polymerized by a twin-screw extruder having a screw diameter of 30 mm and L / D = 36 at a barrel set temperature of 330 ° C., a screw rotation speed of 200 rpm, and a resin supply rate of 6 kg / h. , Polyamide resin (B-1) was obtained.
　The obtained polyamide resin (B-1) has an ultimate viscosity [η] of 0.68 dl / g, a melting point (Tm) not measured, a glass transition temperature (Tg) of 125 ° C., and a heat of fusion (ΔH) of 0 J /. It was g.
[0127]
　(3) Polyamide resin for comparison
　
　Nylon resin manufactured by Toray Co., Ltd., Amylan CM3001-N (66 nylon, extreme viscosity [η]: 1.6 dl / g, melting point (Tm): 262 ° C. , Glass transition temperature (Tg): 53 ° C.)
[0128]
　
　Metaxylylene adipamide resin (manufactured by Mitsubishi Engineering Plastics, Polyamide MXD6 Lenny "# 6002", melting point (Tm): 243 ° C., heat of fusion (ΔH): 52 J / mg)
[0129]
　The extreme viscosities [η], melting point (Tm) and glass transition temperature (Tg) of the obtained polyamide resins (A-1) to (A-5) and (B-1), and the amount of terminal amino groups are as follows. Measured by method.
[0130]
　[Ultimate Viscosity [η]] According to
　JIS K6810-1977, 0.5 g of polyamide resin was dissolved in 50 ml of 96.5% sulfuric acid solution to prepare a sample solution. The number of seconds of flow of the obtained sample solution was measured using a Ubbelohde viscometer under the condition of 25 ± 0.05 ° C. The measurement result was applied to the following formula to calculate the ultimate viscosity [η] of the polyamide resin.
　[Η] = ηSP / [C (1 + 0.205 ηSP)]
　ηSP = (t-t0) / t0 [η]: Extreme viscosity (dl / g)
　ηSP: Specific viscosity
　C: Sample concentration (g / dl)
　t: Sample Solution flow seconds (seconds)
　t0: Blank sulfuric acid flow seconds (seconds)
[0131]
　[Melting point (Tm), glass transition temperature (Tg), heat of fusion (ΔH)] For
　the melting point (Tm) and glass transition temperature (Tg) of the polyamide resin, use a differential scanning calorimeter (DSC220C type, manufactured by Seiko Instruments). Measured using. Specifically, about 5 mg of the polyamide resin was sealed in an aluminum pan for measurement and heated from room temperature to 350 ° C. at 10 ° C./min. The resin was held at 350 ° C. for 5 minutes and then cooled to 30 ° C. at 10 ° C./min to completely melt the resin. After standing at 30 ° C. for 5 minutes, the second heating was performed at 10 ° C./min to 350 ° C. The temperature (° C.) of the heat absorption peak in this second heating was defined as the melting point (Tm) of the polyamide resin, and the displacement point corresponding to the glass transition was defined as the glass transition temperature (Tg). The heat of fusion (ΔH) was determined from the area of ​​the exothermic peak of crystallization in the first heating process according to JIS K7122.
[0132]
　[Amount of terminal amino group]
　1 g of polyamide resin was dissolved in 35 mL of phenol, and 2 mL of methanol was mixed to prepare a sample solution. Then, using thymol blue as an indicator, titration was performed on the sample solution using a 0.01-defined HCl aqueous solution from blue to yellow, and the amount of terminal amino groups ([NH 2 ], unit: mmol /. kg) was measured.
[0133]
　The compositions and properties of the polyamide resins (A-1) to (A-5) and (B-1) and the comparative polyamide resins (a-1) to (a-2) are summarized in Table 1. The numerical values ​​in parentheses in Table 1 indicate the mol% of each diamine or dicarboxylic acid when the total amount of diamine or dicarboxylic acid is 100 mol%.
[0134]
[table 1]

[0135]
　(4) Light-transmitting dye (C)
　8701H: e-BIND LTW-8701H (polyamide 66 and master batch of light-transmitting dye (50% by mass of light-transmitting dye)) manufactured by Orient Chemical Industries, Ltd.
[0136]
　Comparative compound (dye that does not transmit to laser light): Nubian Black TH-827, manufactured by Orient Chemical Industries, Ltd.
[0137]
　(5) Fibrous filler (D)
　Glass fiber (GF): ECS03T-747H Made by Nippon Denki Glass Co., Ltd., average fiber diameter 9.5 to 10.5 μm, cut length 3 mm
　The average fiber length and average fiber diameter of glass fiber , Measured as follows.
[0138]
　(Average fiber length, average fiber diameter)
　Any 100 fiber lengths and fiber diameters of the glass fibers were measured at 50 times using a scanning electron microscope (SEM). Then, the average value of the obtained fiber lengths was taken as the average fiber length, and the average value of the obtained fiber diameters was taken as the average fiber diameter. The aspect ratio was average fiber length / average fiber diameter.
[0139]
　(6) Other components (E)
　Talc (nuclear agent): Average particle size 1.6 μm
[0140]
　2. 2. Preparation / Evaluation of Polyamide Resin Compositions
　
　( Preparation of Polyamide Resin Compositions (PA1-1) to (PA1-13))
　Compositions shown in Table 2. By ratio, the polyamide resin, light-transmitting dye (C), fibrous filler (D) and other components (E) are mixed with a tumbler blender and used in a twin-screw extruder (TEX30α manufactured by Japan Steel Works, Ltd.). Then, melt kneading was performed at a cylinder temperature (melting point (Tm) of the polyamide resin (A) + 15) ° C. The light-transmitting dye (C) was added in the state of the masterbatch, and the amount of the masterbatch added was the value shown in Table 2. Then, the melt-kneaded resin was extruded into a strand and cooled in a water tank. Then, the strand was taken up with a pelletizer and cut to obtain a pellet-shaped polyamide resin composition (light-transmitting resin composition).
[0141]
　 A
　polyamide resin composition was obtained in the same manner as in Example 3 except that the light-transmitting dye (C) was changed to the above-mentioned comparative compound (Nubian Black TH-827, manufactured by Orient Chemical Industries, Ltd.). ..
[0142]
　Melting point (Tm), glass transition temperature (Tg), laser light transmittance, deflection temperature under load, tensile strength, and corrected heat of fusion of the obtained polyamide resin composition (light-transmitting resin composition other than Comparative Example 5). ([Delta] H R a) was measured by the following method.
[0143]
　[Melting Point (Tm), Glass Transition Temperature (Tg)] The melting point (Tm) and glass transition temperature (Tg) of the
　obtained polyamide resin composition were measured by the same method as described above.
[0144]
　[Transmittance of Laser Light] The
　obtained polyamide resin composition is molded using the following injection molding machine under the following molding conditions to obtain a test piece having a length of 125 mm, a width of 13 mm, and a thickness of 1.6 mm. It was.
　Molding machine: EC75N-2 (A)
　molding machine manufactured by Toshiba Machine Co., Ltd. Cylinder temperature: Melting point (Tm) + 10 ° C
　of polyamide resin composition Mold temperature: Glass transition temperature (Tg) -5 ° C
　injection of polyamide resin composition The
　same applies to the measurement at the set speed: 50 mm / sec or less.
　Then, the transmittance of the laser light at a wavelength of 940 nm of the obtained test piece was measured using a power meter F300-SH manufactured by Ophir.
[0145]
　[Deflection temperature under load]
　A test piece having a thickness of 3.2 mm was obtained under the following molding conditions using the following injection molding machine.
　　Molding machine: Sodick Plastic Co., Ltd., Tupar TR40S3A
　　Molding machine Cylinder temperature: Melting point of polyamide resin composition (Tm) + 15 ° C.
　　Mold temperature: Glass transition temperature of polyamide resin composition (Tg) + 20 ° C.
　Next, the test obtained. The piece is set in a deflection temperature tester under load, the span is fixed at 100 mm, and a pressure of 1.8 MPa is applied from 35 ° C. at a heating rate of 120 ° C./hr to reach the temperature at which the amount of deflection reaches 0.254 mm. Was defined as the "deflection temperature under load".
[0146]
　[Tensile Strength] The
　obtained polyamide resin composition was molded under the following molding conditions using the following injection molding machine to obtain an ASTM dumbbell type test piece Type I having a thickness of 3.2 mm.
　(Molding conditions)
　Molding machine: Sumitomo Heavy Industries, Ltd. SG50M3
　molding machine cylinder temperature: melting point (Tm) + 10 ° C. of the polyamide resin composition
　Mold temperature: 120 ° C.
　Injection Set Speed: 60 mm / sec
　and the resulting test piece, It was left at a temperature of 23 ° C. and in a nitrogen atmosphere for 24 hours. Next, a tensile test was performed in an atmosphere of a temperature of 23 ° C. and a relative humidity of 50% in accordance with ASTMD638, and the tensile strength was measured.
[0147]
　[Correction heat of fusion ([Delta] H R )] 　in the same manner as the test in a tensile strength piece, a test piece was obtained. When 5 mg of a part of the obtained test piece was taken out and heated at 10 ° C./min using a differential scanning calorimeter (DSC220C type, manufactured by Seiko Instruments Inc.), heat was generated in the first heating process. The heat of fusion (ΔH) was calculated from the area of ​​the peak. The resulting heat of fusion of ([Delta] H), divided by the ratio of the total weight of components other than the fibrous filler (D) to the total weight of the polyamide resin composition, the correction amount of heat of fusion ([Delta] H R were calculated).
[0148]
　Table 2 shows the evaluation results of Examples 1 to 10, Reference Example 1 and Comparative Examples 1 and 2.
[0149]
[Table 2]

[0150]
　As shown in Table 2, all of the polyamide resin compositions of Examples 1 to 10 have a higher deflection temperature under load and higher heat resistance than the polyamide resin compositions of Comparative Examples 1 and 2 and Reference Example 1. You can see that. In addition, the polyamide resin compositions of Examples 4, 9 and 10 all have laser light transmittance and tensile strength equal to or higher than those of the polyamide resin compositions of Comparative Examples 1 and 2 and Reference Example 1. I understand.
[0151]
　Among them, moderately lowering the crystallinity of the polyamide resin (A) (it may be contained isophthalic acid, branched or contain a aliphatic diamine) that is, corrected heat of fusion of the polyamide resin composition ([Delta] H R a) It can be seen that the welding strength is likely to be further increased by making the welding strength moderately low (comparison with Examples 4, 9 and 10).
[0152]
　Also, to be (often enough not too high) moderately increasing the content of the fibrous filler (D) in the polyamide resin composition, the correction amount of heat of fusion of the polyamide resin composition ([Delta] H R lowering the)
[0153]
　Further, the content of the light transmitting dye (C) in the polyamide resin composition, by increasing the extent of not too high, the correction amount of heat of fusion of the polyamide resin composition ([Delta] H R a) low, the welding strength more It can be seen that it is easy to increase (comparison with Examples 3 to 5).
[0154]
　Further, the polyamide resin composition of Comparative Example 5 in which a comparative compound was used instead of the light-transmitting dye (C) absorbed (not transmitted) laser light, and generated heat and ignited. Therefore, the transmittance of the laser light could not be measured, and no other measurement was performed.
[0155]
　3. 3. Preparation / Evaluation of 　Welded Body
　
( Preparation of light-absorbing resin compositions (PA2-1) to (PA2-9))
　Shown in the lower part of Table 3. Polyamide resin, light-absorbing dye, fibrous filler and nucleating agent are mixed with a tumbler blender at the desired composition ratio, and the cylinder temperature (polyamide resin (Polyamide resin) It was melt-kneaded at the melting point (Tm) of A') + 15) ° C. Then, the melt-kneaded resin was extruded into a strand and cooled in a water tank. Then, the strands were taken up with a pelletizer and cut to obtain a pellet-shaped light-absorbing resin composition.
[0156]
　In the preparation of the light-absorbing resin composition, as the polyamide resin, the above-mentioned polyamide resins (A-1) to (A-5), (B-1), (a-1) to (a-2) Was used. Carbon black (manufactured by Mitsubishi Chemical Corporation, MA600B) was used as the light-absorbing dye. As the fibrous filler, the above-mentioned glass fiber was used. As the nucleating agent, the above-mentioned talc was used.
[0157]
　Then, the welding strength between the molded body of the polyamide resin composition (light-transmitting resin composition) in the upper part of Table 3 and the molded body of the light-absorbing resin composition in the lower part of Table 2 was measured by the following method. ..
[0158]
　[Welding strength]
　(Preparation of molded product) The
　polyamide resin composition (light-transmitting resin composition) and the light-absorbing resin composition were molded by the following injection molding machines under the following molding conditions, respectively. A first molded product (laser light transmitting molded product) and a second molded product (laser light absorbing molded product) having a length of 125 mm, a width of 13 mm, and a thickness of 1.6 mm were obtained.
　Molding machine: EC75N-2 (A)
　molding machine manufactured by Toshiba Machine Co., Ltd. Cylinder temperature: Melting point of polyamide resin (Tm) + 10 ° C
　Mold temperature: Glass transition temperature of polyamide resin (Tg) -5 ° C
　Injection set speed: 50 mm / Sec
[0159]
　(Manufacture of Laser Welded Body)
　FIG. 1 is a schematic diagram showing a method for measuring welding strength. As shown in FIG. 1, one end of the obtained first molded product (light-transmitting resin member) in the length direction and the other end of the second molded product (light-absorbing resin member) in the length direction. The ends of the molded product are overlapped so that the overlapping width (width in the length direction of the molded product) is 1 cm, and the portion 0.5 mm from the end of the first molded product (light-transmitting resin member) is centered. , The overlapping portion was irradiated with laser light within a range of ± 10 mm in the length direction of the molded product. The irradiation conditions of the laser light were as follows.
　Testing machine: Fd-200 manufactured by Fine Devices Co., Ltd. 　Pressurization
　pressure: 0.5 MPa
Laser diameter: 2 mmφ
　Scanning distance: 10 mm
　Total amount of energy reaching the second molded product: 12J
[0160]
　(Measurement of Welding Strength) The
　obtained laser welded body was subjected to a tensile test in an atmosphere of a temperature of 23 ° C. and a relative humidity of 50% in accordance with JIS K6301-2, and the tensile strength was measured. The obtained tensile strength was defined as "welding strength".
[0161]
　The evaluation results of Examples 11 to 22, Reference Example 2 and Comparative Examples 3 to 4 are shown in Table 3.
[0162]
[Table 3]

[0163]
　As shown in Table 3, it can be seen that the welded bodies of Examples 14, 17, 21 and 22 all have higher welding strength than the welded bodies of Comparative Examples 3 and 4. Among them, the correction amount of heat of fusion ([Delta] H of the polyamide resin composition R (lower than, for example, 54J / g))
[0164]
　Further, it can be seen that the welding strength can be further increased by increasing the content of the fibrous filler (D) in the polyamide resin composition to such an extent that it is not too high (comparison with Examples 11, 14 and 16). ..
[0165]
　Further, it can be seen that the welding strength can be further increased by increasing the content of the light-transmitting dye (C) in the polyamide resin composition to such an extent that it is not too high (compared to Examples 13 to 15).
[0166]
　This application claims priority under Japanese Patent Application No. 2018-026310 filed on February 16, 2018. All the contents described in the application specification and drawings are incorporated herein by reference.
Industrial applicability
[0167]
　According to the present invention, a polyamide resin composition having high laser welding property, high mechanical strength and high heat resistance that can exhibit good welding strength at the time of laser welding without lowering the transmission rate of laser light. And a method for producing a welded product using the same can be provided.
The scope of the claims
[Claim 1]
　The polyamide resin (A) having a melting point of 300 ° C. or higher measured by a differential scanning calorimeter (DSC) has 30 to 89.9 parts by mass and
　a melting point measured by a differential scanning calorimetry (DSC). Polyamide resin composition containing 0 to 45 parts by mass of a polyamide resin (B),
　0.1 to 5 parts by mass of a light transmissive dye (C),
　and 10 to 55 parts by mass of a fibrous filler (D). The
　polyamide resin (A) is a component unit (a1) derived from a dicarboxylic acid (however, the total of (A), (B), (C) and (D) is 100 parts by mass ). And the component unit (a2) derived from diamine, and
　the component unit (a1) derived from the dicarboxylic acid is terephthalic acid with respect to a total of 100 mol% of the component unit (a1) derived from the dicarboxylic acid. 20 to 100 mol% of the component unit derived from, 0 to 80 mol of at least one of the component unit derived from an aromatic dicarboxylic acid other than terephthalic acid and the component unit derived from an aliphatic dicarboxylic acid having 4 to 20 carbon atoms. The
　component unit (a2) derived from the diamine is at least one of a component unit derived from an aliphatic diamine having 4 to 15 carbon atoms and a component unit derived from an alicyclic diamine having 4 to 20 carbon atoms. The
　amount of heat of fusion (ΔH) of the polyamide resin composition measured by a differential scanning calorimeter (DSC) is the sum of the components other than the fibrous filler (D) with respect to the total mass of the polyamide resin composition. correction heat of fusion obtained by dividing the ratio of the mass ([Delta] H R ) is 10 ~ 70 J / g,
　A polyamide resin composition in which the transmittance of laser light having a wavelength of 940 nm at a thickness of 1.6 mm is 15% or more of the molded product of the polyamide resin composition.
[Claim 2]
　As for the component unit (a2) derived from the diamine, the component unit derived from the aliphatic diamine having 4 to 15 carbon atoms is 50 to 50 to 100 mol% in total of the component unit (a2) derived from the diamine.
　The polyamide resin composition according to claim 1, which contains 100 mol% .
[Claim 3]

　The polyamide resin composition according to claim 2, 　wherein the component unit derived from the aliphatic diamine having 4 to 15 carbon atoms contains a component unit derived from a linear aliphatic diamine having 4 to 8 carbon atoms .
[Claim 4]

　The polyamide resin composition according to claim 3, 　wherein the component unit derived from the linear aliphatic diamine having 4 to 8 carbon atoms is a component unit derived from an alkylene diamine having 4 to 8 carbon atoms .
[Claim 5]

　The polyamide resin composition according to claim 4, 　wherein the component unit derived from the alkylenediamine having 4 to 8 carbon atoms is a component unit derived from 1,6-hexanediamine .
[Claim 6]

　The polyamide resin composition according to claim 1, 　wherein the component unit derived from the dicarboxylic acid (a1) further contains a component unit derived from isophthalic acid .
[Claim 7]
　The polyamide resin (B) contains a component unit (b1) derived from a dicarboxylic acid and a component unit (b2) derived from a diamine, and the component unit (b1) derived from the
　dicarboxylic acid is derived from isophthalic acid. 　The polyamide resin composition according to claim 1 ,
　wherein the component unit (b2) derived from the diamine contains a component unit derived from an aliphatic diamine having 4 to 15 carbon atoms
.
[Claim 8]
　The component unit derived from the dicarboxylic acid (b1) may further contain
　a component unit derived from terephthalic acid, and the molar ratio of the component unit derived from isophthalic acid to the component unit derived from the terephthalic acid is
　The polyamide resin composition according to claim 7, wherein the component unit derived from the isophthalic acid / the component unit derived from the terephthalic acid = 55/45 to 100/0 (molar ratio) .
[Claim 9]

　The polyamide according to claim 1, 　wherein the content of the fibrous filler (D) is 40 parts by mass or less with respect to a total of 100 parts by mass of (A), (B), (C) and (D). Resin composition.
[Claim 10]
　A light-transmitting resin composition for laser welding, which comprises the polyamide resin composition according to claim 1.
[Claim 11]
　A molded product obtained by molding the polyamide resin composition according to claim 1.
[Claim 12]
　The step of molding the polyamide resin composition according to claim 1 to obtain a first molded product, and the second molded product obtained by molding
　a light absorbing resin composition containing a thermoplastic resin and a light absorbing dye. obtaining a,
　wherein the first molded body superimposed and a second molded body, the first by irradiating a laser beam through the molded body, welded to said second molded body and said first molded body A method for producing a laser welded product, which comprises a step of forming a laser welded product.
[Claim 13]
　The
　method for producing a laser welded body according to claim 12, wherein the thermoplastic resin is a polyamide resin .
[Claim 14]
　The
　method for producing a laser welded body according to claim 13, wherein the polyamide resin is the same as the polyamide resin (A) contained in the polyamide resin composition .