JP7300571B2 - Polyamide resin composition, molded article, kit, and method for producing molded article - Google Patents

Description

TECHNICAL FIELD The present invention relates to a polyamide resin composition, a molded article, a kit, and a method for producing a molded article. The polyamide resin composition of the present invention is mainly used as a light-transmitting resin composition (light-transmitting resin composition) for laser welding.

Polyamide resins, which are typical engineering plastics, are easy to process and have excellent mechanical properties, electrical properties, heat resistance, and other physical and chemical properties. Therefore, it is widely used for vehicle parts, electrical/electronic equipment parts, and other precision equipment parts. Recently, parts with complicated shapes are also being manufactured with polyamide resin. For example, various welding techniques such as adhesive welding, adhesive welding, Vibration welding, ultrasonic welding, hot plate welding, injection welding, laser welding techniques, etc. are used.

However, welding with an adhesive poses a problem of environmental load such as pollution of surroundings in addition to time loss until curing. Problems with ultrasonic welding and hot plate welding have been pointed out, such as damage to the product due to vibration and heat, and the need for post-processing due to the generation of abrasion powder and burrs. In addition, injection welding often requires a special mold or molding machine, and furthermore, it cannot be used unless the fluidity of the material is good.

On the other hand, in laser welding, a resin member (hereinafter sometimes referred to as "transmissive resin member") having transparency (also referred to as non-absorbing or weak absorption) to laser light and a resin member having absorption to laser light are combined. (hereinafter sometimes referred to as "absorbing resin member") are brought into contact with each other and welded to join the two resin members together. Specifically, it is a method of irradiating the joint surface with a laser beam from the transmissive resin member side and melting and joining the absorbing resin member forming the joint surface with the energy of the laser beam. Laser welding does not generate abrasion powder or burrs and causes little damage to products.In addition, polyamide resin itself is a material with relatively high laser transmittance, so processing of polyamide resin products by laser welding technology is It's been getting a lot of attention lately.

The transmissive resin member is usually obtained by molding a light transmissive resin composition. As such a light-transmitting resin composition, in Patent Document 1, (A) 100 parts by weight of polyamide resin, (B) a reinforcing filler having a refractive index at 23 ° C. of 1.560 to 1.600 A polyamide resin composition containing 1 to 150 parts by weight, wherein at least one monomer constituting at least one of the (A) polyamide resins contains an aromatic ring. A welding polyamide resin composition is described.

JP 2008-308526 A

Here, when blending glass fibers with a polyamide resin, the glass fibers are usually treated with a sizing agent or a surface treatment agent. As a result of investigation by the inventor, it was found that the light transmittance may deteriorate depending on the type of the sizing agent and the surface treatment agent. An object of the present invention is to solve such problems, and an object thereof is to provide a polyamide resin composition excellent in light transmittance, a molded article, a kit, and a method for producing the molded article.

Under the above-mentioned problems, the present inventors have conducted studies and found that by using glass fibers containing at least one of a specific xylylenediamine-based polyamide resin, a specific sizing agent, and a surface treatment agent, light transmittance can be increased. It was found that it is possible to maintain
Specifically, the above problems have been solved by the following means.
<1> Composed of diamine-derived structural units and dicarboxylic acid-derived structural units, more than 60 mol% of the diamine-derived structural units are derived from meta-xylylenediamine, and 70 mol% or more of the dicarboxylic acid-derived structural units are A glass containing 40 to 80% by mass of a polyamide resin derived from an α,ω-straight-chain aliphatic dicarboxylic acid having 4 to 20 carbon atoms, and further containing a light transmitting dye and at least one of a sizing agent and a surface treatment agent. A polyamide resin composition comprising 1 to 20% by mass of isophorone diisocyanate in the gas component obtained by heating at least one of the sizing agent and the surface treatment agent at 280° C. for 1 hour.
<2> The polyamide resin composition according to <1>, wherein the sizing agent and the surface treatment agent contain at least one of a urethane-based sizing agent and a silane coupling agent.
<3> The polyamide resin composition according to <1> or <2>, wherein the blending amount of the glass fiber is 25% by mass or more of the polyamide resin composition.
<4> The polyamide resin composition according to any one of <1> to <3>, wherein 70 mol% or more of the constituent units derived from the dicarboxylic acid are derived from sebacic acid.
<5> A molded article formed from the polyamide resin composition according to any one of <1> to <4>.
<6> A kit comprising the resin composition according to any one of <1> to <4>, and a light-absorbing resin composition containing a thermoplastic resin and a light-absorbing dye.
<7> The resin composition and the light-absorbing resin composition are respectively molded into ASTM standard No. 4 pieces with a thickness of 1.5 mm, and pressed in galvanomirror scanning fiber laser welding. The kit according to <6>, having a tensile strength of 1400 N or more at a pressure of 600 N, a laser beam diameter of 2 mm, a laser welding width of 16 mm, and a total energy input for welding of 160 J.
<8> A molded article obtained by molding the resin composition according to any one of <1> to <4>, and a light-absorbing resin composition containing a thermoplastic resin and a light-absorbing dye is molded. A method of manufacturing a molded product, comprising laser welding a molded product comprising:
<9> A molded article obtained by molding the resin composition according to any one of <1> to <4> or the kit according to <6> or <7>.

ADVANTAGE OF THE INVENTION By this invention, it became possible to provide the polyamide resin composition and molded article which were excellent in light transmittance. In particular, it has become possible to provide a transmissive resin member for laser welding that is excellent in light transmittance.

It is the schematic which shows the state which welded the ASTM No. 4 dumbbell piece.

The contents of the present invention will be described in detail below. In this specification, the term "~" is used to mean that the numerical values before and after it are included as the lower limit and the upper limit.

The polyamide resin composition of the present invention is composed of diamine-derived structural units and dicarboxylic acid-derived structural units, and more than 60 mol% of the diamine-derived structural units are derived from meta-xylylenediamine, and dicarboxylic acid-derived structural units. 70 mol% or more of the polyamide resin derived from α, ω-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms is contained in 40 to 80% by mass, and further, a light transmitting dye, a sizing agent and a surface treatment agent. At least one of the sizing agent and the surface treatment agent is heated at 280° C. for 1 hour, and the proportion of isophorone diisocyanate is 1 to 20% by mass in the gas component. characterized by
With such a configuration, a polyamide resin composition having excellent light transmittance (in particular, light transmittance at a wavelength of 1070 nm) can be obtained. Furthermore, it should be excellent in light absorption member and adhesiveness.

<Polyamide resin>
The polyamide resin composition of the present invention is composed of diamine-derived structural units and dicarboxylic acid-derived structural units, and more than 60 mol% of the diamine-derived structural units are derived from meta-xylylenediamine, and dicarboxylic acid-derived structural units. 70 mol% or more of the polyamide resin derived from α,ω-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms. In this specification, the polyamide resin may be referred to as a xylylenediamine-based polyamide resin.

In the xylylenediamine-based polyamide resin used in the present invention, preferably 63 mol % or more, more preferably 65 mol % or more of diamine-derived constitutional units are derived from meta-xylylenediamine. The upper limit of the meta-xylylenediamine-derived structural unit in the diamine-derived structural unit is 100 mol%, but it is 95 mol% or less, 90 mol% or less, 80 mol% or less, and 75 mol% or less. may By using m-xylylenediamine as more than 60 mol % of the structural units derived from diamine, particularly excellent light transmittance can be achieved.

Examples of diamines other than meta-xylylenediamine that can be used as a raw material diamine component for xylylenediamine-based polyamide resins include paraxylylenediamine, tetramethylenediamine, pentamethylenediamine, 2-methylpentanediamine, hexamethylenediamine, and heptamethylene. Aliphatic diamines such as diamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, dodecamethylenediamine, 2,2,4-trimethyl-hexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 1,3- bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, bis(4-aminocyclohexyl)methane, 2,2-bis(4-amino cyclohexyl) propane, bis (aminomethyl) decalin, bis (aminomethyl) tricyclodecane and other alicyclic diamines, bis (4-aminophenyl) ether, paraphenylenediamine, bis (aminomethyl) naphthalene and other aromatic rings can be exemplified, and can be used alone or in combination of two or more. In the present invention, para-xylylenediamine is preferred as the diamine other than meta-xylylenediamine.

As one embodiment of the diamine-derived structural unit of the present invention, a structural unit derived from more than 60 mol % of meta-xylylenediamine and 40 to 0 mol % of para-xylylenediamine is exemplified. Structural units derived from ~100 mol% and 37 to 0 mol% of para-xylylenediamine are preferred, and structural units derived from 65 to 95 mol% of meta-xylylenediamine and 35 to 5 mol% of para-xylylenediamine are more preferred. Structural units derived from 65 to 80 mol % of meta-xylylenediamine and 35 to 20 mol % of para-xylylenediamine are more preferable. In the above embodiment, the total amount of structural units derived from meta-xylylenediamine and structural units derived from para-xylylenediamine preferably accounts for 90 mol% or more of the structural units derived from diamine, and may account for 95 mol% or more. More preferably, it accounts for 99 mol % or more.

The xylylenediamine-based polyamide resin used in the present invention preferably contains 75 mol% or more, more preferably 85 mol% or more, still more preferably 95 mol% or more, and still more preferably 99 mol% of dicarboxylic acid-derived structural units. The above is derived from α,ω-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms (preferably sebacic acid). The upper limit of the α,ω-straight-chain aliphatic dicarboxylic acid-derived structural units having 4 to 20 carbon atoms in the dicarboxylic acid-derived structural units is 100 mol %.

The α,ω-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms is preferably α,ω-linear aliphatic dicarboxylic acid having 8 to 20 carbon atoms, and α,ω having 8 to 12 carbon atoms. - straight-chain aliphatic dicarboxylic acids are more preferred, and sebacic acid is even more preferred.
Examples of α,ω-linear aliphatic dicarboxylic acids having 4 to 20 carbon atoms include succinic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid, adipic acid, sebacic acid, undecanedioic acid, and dodecanedioic acid. can be exemplified, and can be used alone or in combination of two or more. Sebacic acid is preferred as the α,ω-straight-chain aliphatic dicarboxylic acid having 4 to 20 carbon atoms.

Examples of dicarboxylic acid components other than the α,ω-straight-chain aliphatic dicarboxylic acids having 4 to 20 carbon atoms include phthalic acid compounds such as isophthalic acid, terephthalic acid and orthophthalic acid, 1,2-naphthalenedicarboxylic acid, 1,3 -naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 1,6-naphthalenedicarboxylic acid, 1,7-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2,3-naphthalene Naphthalenedicarboxylic acid isomers such as dicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and 2,7-naphthalenedicarboxylic acid can be exemplified, and one or a mixture of two or more thereof can be used.

The xylylenediamine-based polyamide resin is mainly composed of diamine-derived structural units and dicarboxylic acid-derived structural units, but does not completely exclude structural units other than these, such as ε-caprolactam and laurolactam. Needless to say, structural units derived from lactams such as lactams and aliphatic aminocarboxylic acids such as aminocaproic acid and aminoundecanoic acid may be included. The term "main component" as used herein means that among the constituent units constituting the xylylenediamine-based polyamide resin, the total number of constituent units derived from diamine and constituent units derived from dicarboxylic acid is the largest among all constituent units. In the present invention, the sum of diamine-derived structural units and dicarboxylic acid-derived structural units in the xylylenediamine-based polyamide resin preferably accounts for 90% or more of all structural units, more preferably 95% or more. .

The melting point of the polyamide resin is preferably 150 to 350°C, more preferably 180 to 330°C, even more preferably 190 to 300°C, and even more preferably 200 to 280°C.
The melting point can be measured according to JIS K7121 and K7122 according to differential scanning calorimetry.

Polyamide resin, the lower limit of the number average molecular weight (Mn) is preferably 6,000 or more, more preferably 8,000 or more, more preferably 10,000 or more, 15,000 or more more preferably, 20,000 or more, and even more preferably 22,000 or more. The upper limit of Mn is preferably 35,000 or less, more preferably 30,000 or less, even more preferably 28,000 or less, and even more preferably 26,000 or less. Within such a range, heat resistance, elastic modulus, dimensional stability, and moldability are improved.

The resin composition of the present invention contains a xylylenediamine-based polyamide resin in a proportion of 40 to 80% by mass of the resin composition. The xylylenediamine-based polyamide resin is preferably contained in a proportion of 45% by mass or more of the resin composition, and may be contained in a proportion of 50% by mass or more, particularly 55% by mass or more. In addition, the upper limit of the content of the xylylenediamine-based polyamide resin is preferably 75% by mass or less, more preferably 70% by mass or less, 65% by mass or less, and 60% by mass. It may be included in the following proportions.
The xylylenediamine-based polyamide resin may contain only one type, or may contain two or more types. When two or more kinds are included, the total amount is preferably within the above range.

<Other resin components>
The polyamide resin composition of the present invention may contain a polyamide resin other than the xylylenediamine-based polyamide resin and a thermoplastic resin other than the polyamide resin.
Polyamide resins other than the xylylenediamine-based polyamide resins include polyamide 6, polyamide 66, polyamide 11, polyamide 12, polyamide 6T, polyamide 9T, polyamide 10T, polyamide 6I, polyamide 9I, polyamide 6T/6I, and polyamide 9T/9I. etc. are exemplified.
When the polyamide resin composition of the present invention contains a polyamide resin other than the xylylenediamine-based polyamide resin, the content thereof is preferably 5 to 30% by mass of the resin component contained in the composition.
On the other hand, the polyamide resin composition of the present invention may be configured so as not to substantially contain polyamide resins other than the xylylenediamine-based polyamide resin. The term "substantially free" means that the content of the polyamide resin other than the xylylenediamine-based polyamide resin is less than 5% by mass of the resin component contained in the composition, and may be 3% by mass or less. Preferably, it is 2% by mass or less.

Examples of thermoplastic resins other than polyamide resins include polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polycarbonate resins, and polyacetal resins. The polyamide resin composition of the present invention can also be configured so as not to substantially contain resin components other than the polyamide resin. "Substantially free" means that the content of resin components other than the polyamide resin is less than 5% by mass of the resin components contained in the composition, preferably 3% by mass or less, and 2% by mass. The following are more preferable.

<Glass fiber>
The polyamide resin composition of the present invention contains glass fibers.
The glass fiber is composed of glass such as A-glass, C-glass, E-glass, and S-glass, and E-glass (alkali-free glass) is particularly preferable because it does not adversely affect the polycarbonate resin.
The glass fiber refers to a fiber having a perfect circular or polygonal cross-sectional shape when cut at right angles to the length direction and exhibiting a fibrous appearance.

The glass fiber used in the polyamide resin composition of the present invention may be a single fiber or a plurality of twisted single fibers.
The forms of glass fibers are "glass roving" which is continuously wound from a single fiber or multiple strands, "chopped strand" which is cut to a length of 1 to 10 mm, and "milled strand" which is pulverized to a length of 10 to 500 μm. fiber". Such glass fibers are commercially available from Asahi Fiber Glass Co., Ltd. under the trade names of "Glasslon Chopped Strand" and "Glasslon Milled Fiber" and are readily available. Glass fibers having different forms can be used together.

Further, in the present invention, the glass fiber preferably has a modified cross-sectional shape. This irregular cross-sectional shape means that the oblateness indicated by the length/breadth ratio (D2/D1), where D2 is the length of the cross section perpendicular to the length direction of the fiber, and D1 is the width of the fiber, is, for example, 1. 5 to 10, preferably 2.5 to 10, more preferably 2.5 to 8, and particularly preferably 2.5 to 5. Regarding such flat glass, the description in paragraphs 0065 to 0072 of JP-A-2011-195820 can be referred to, and the contents thereof are incorporated herein.

The amount of glass fiber in the polyamide resin composition of the present invention is 25% by mass or more of the polyamide resin composition, preferably 28% by mass or more, 35% by mass or more, and even if it is 45% by mass or more good. Although the upper limit is not particularly defined, it is preferably 65% by mass or less, more preferably 60% by mass or less, even more preferably 55% by mass or less, and may be 45% by mass or less. The polyamide resin composition of the present invention may contain only one type of glass fiber, or may contain two or more types. When two or more kinds are included, the total amount is within the above range. The amount of the glass fiber compounded in the present invention is meant to include the amount of the sizing agent and the surface treatment agent.
In the polyamide resin composition of the present invention, the total of the xylylenediamine-based polyamide resin and the glass fiber preferably accounts for 80% by mass or more of the composition, more preferably 85% by mass or more, and 90% by mass or more. and more preferably 95% by mass or more.
Further, in the polyamide resin composition of the present invention, the total of the xylylenediamine-based polyamide resin, the glass fiber and the light-transmitting dye preferably accounts for 84% by mass or more of the composition, and may account for 89% by mass or more. More preferably, it accounts for 94% by mass or more, and even more preferably 99% by mass or more.

<Sizing agent and surface treatment agent>
The polyamide resin composition of the present invention contains 1 to 20% by mass of isophorone diisocyanate in the gas component obtained by heating at least one of the sizing agent and the surface treatment agent at 280° C. for 1 hour. Light transmittance can be improved by using at least one of such glass fiber sizing agents and surface treatment agents, and by using a predetermined polyamide resin. The proportion of isophorone diisocyanate is preferably 15% by mass or less, more preferably 12% by mass or less, and may be 10% by mass or less. Although the lower limit is not particularly defined, it is, for example, 2% by mass or more, and may be 5% by mass or more.
Here, the ratio of isophorone diisocyanate in the gas component obtained by heating at 280° C. for 1 hour is the value measured by the method described in Examples below. However, for a device that performs TD-GC/MS analysis, values measured using other similar analysis devices may be used. If there is a difference in value between the analyzer described in this embodiment and another gas analyzer of the same type, the value of the gas analyzer described in this embodiment is used as the value in the present invention.
In the present invention, at least one of the sizing agent and surface treatment agent is preferably a urethane-based sizing agent and a silane coupling agent.

A wide range of known urethane sizing agents can be used, and a urethane sizing agent obtained from an alcohol-derived polyol and isocyanate is more preferable.
Alcohols that form alcohol-derived polyols include ethylene glycol, propylene glycol, 1.3-propanediol, 1.4-butanediol, 1.5-pentanediol, 1.6-hexanediol, neopentyl glycol, and diethylene glycol. , triethylene glycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol, tripropylene glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, bisphenol A, hydroquinone and their alkylene oxide adducts, glycerin, tri Methylolethane, trimethylolpropane, pentaerythritol, sorbitol and the like.
The isocyanate is preferably an alicyclic or aliphatic isocyanate such as tetramethylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine isocyanate, isophorone diisocyanate, 1,3-cyclopentylene diisocyanate, 1,3-cyclohexylene. Diisocyanate, 1.4-cyclohexylene diisocyanate, 1.3-di(isocyanatomethyl)cyclohexane, 1.4-di(isocyanatomethyl)cyclohexane, 4.4'-dicyclohexylmethane diisocyanate, trimer compounds thereof, and the like. be done.

Specific examples of silane coupling agents include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β (aminoethyl)γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl)γ - aminosilane coupling agents such as aminopropyltrimethoxysilane, N-β (aminoethyl)γ-aminopropyltriethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltrimethoxysilane, Epoxysilane coupling agents such as γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacryloxy Examples include methacryloxisilane coupling agents such as propyltriethoxysilane, and vinylsilane coupling agents such as vinyltrimethoxysilane, vinyltriethoxysilane, and vinyltris(β-methoxyethoxy)silane.
These sizing agents and surface treatment agents can be used alone or as a mixture of two or more. The total amount of the sizing agent and surface treatment agent is preferably 0.01 to 4.0% by mass, more preferably 0.1 to 2.0% by mass of the glass fiber.

<Light-transmitting dye>
The light-transmitting dyes used in the present invention are usually black dyes, and specific examples include nigrosine, naphthalocyanine, aniline black, phthalocyanine, porphyrin, perinone, quaterylene, azo dyes, anthraquinone, pyrazolone, squaric acid derivatives, and immonium dyes, and the like.
Commercially available products include e-BIND LTW-8731H and e-BIND LTW-8701H, which are colorants manufactured by Orient Chemical Industry Co., Ltd.; 5602, and Macrolex Yellow 3G, Macrolex Red EG, and Macrolex Green 3, which are colorants manufactured by LANXESS.
In particular, when a polyamide resin composition containing at least one of pyrazolone, perinone and anthraquinone is used as the light-transmitting dye, color transfer of the resulting molded article after a wet heat test can be effectively suppressed.
The content of the light-transmitting dye in the polyamide resin composition of the present invention is preferably 0.001 parts by mass or more, more preferably 0.006 parts by mass or more, relative to 100 parts by mass of the resin composition. Preferably, it may be 0.018 parts by mass or more, 0.024 parts by mass or more, 0.030 parts by mass or more, or 0.050 parts by mass or more. Further, the upper limit of the content of the light-transmitting dye is preferably 5.0 parts by mass or less, more preferably 3.0 parts by mass or less, and 1.0 parts by mass or less of the resin composition. 0.20 mass parts or less, 0.10 mass parts or less, or 0.060 mass parts or less may be sufficient.
Only one kind of light-transmitting dye may be contained, or two or more kinds thereof may be contained. When two or more kinds are included, the total amount is preferably within the above range.
Moreover, the polyamide resin composition of the present invention preferably does not substantially contain carbon black. "Not substantially contained" means, for example, 0.0001% by mass or less of the resin composition.

<Nucleating agent>
The polyamide resin composition of the present invention may contain a nucleating agent in order to adjust the crystallization rate. The type of nucleating agent is not particularly limited, but talc, boron nitride, mica, kaolin, calcium carbonate, barium sulfate, silicon nitride, potassium titanate and molybdenum disulfide are preferred, and talc and boron nitride are more preferred. Preferred, and more preferred is talc.
When the polyamide resin composition of the present invention contains a nucleating agent, the content thereof is preferably 0.01 to 10 parts by mass, preferably 0.1 to 8 parts by mass, based on 100 parts by mass of the xylylenediamine-based polyamide resin. parts is more preferred, and 0.1 to 6 parts by mass is even more preferred.
The polyamide resin composition of the present invention may contain only one type of nucleating agent, or may contain two or more types of nucleating agents. When two or more types are included, the total amount is preferably within the above range.

<Stabilizer>
The polyamide resin composition of the present invention may contain stabilizers (antioxidants, heat stabilizers).
Examples of stabilizers include copper compounds (such as CuI), alkali halides (such as KI), hindered heat stabilizers, and fatty acid metal salts (such as zinc stearate).
Details of the stabilizer can be referred to paragraphs 0018 to 0020 of JP-A-2016-074804, the contents of which are incorporated herein.

When the polyamide resin composition of the present invention contains a stabilizer, the content thereof is preferably 0.01 to 5 parts by mass, preferably 0.08 to 3 parts by mass, with respect to 100 parts by mass of the xylylenediamine-based polyamide resin. parts is more preferred, and 0.1 to 1 part by mass is even more preferred.
The polyamide resin composition of the present invention may contain only one type of stabilizer, or may contain two or more types of stabilizers. When two or more types are included, the total amount is preferably within the above range.

<Release agent>
The polyamide resin composition of the present invention may contain a release agent.
Examples of release agents include aliphatic carboxylic acids, salts of aliphatic carboxylic acids, esters of aliphatic carboxylic acids and alcohols, aliphatic carboxylic acid amides, and aliphatic hydrocarbon compounds having a number average molecular weight of 200 to 15,000. , and polysiloxane-based silicone oils.
Details of the release agent can be referred to paragraphs 0034 to 0039 of JP-A-2017-115093, and the contents thereof are incorporated herein.

When the polyamide resin composition of the present invention contains a release agent, the content thereof is preferably 0.05 to 1 part by mass with respect to 100 parts by mass of the xylylenediamine-based polyamide resin, and 0.1 to 0 0.8 parts by weight is more preferred, and 0.2 to 0.6 parts by weight is even more preferred.
The polyamide resin composition of the present invention may contain only one release agent, or may contain two or more release agents. When two or more types are included, the total amount is preferably within the above range.

<Other ingredients>
The polyamide resin composition of the present invention may contain other components within the scope of the present invention. Examples of such additives include fillers other than glass fibers, light stabilizers, antioxidants, flame retardants other than phosphazene flame retardants, flame retardant aids other than zinc metal oxide, ultraviolet absorbers, and fluorescent brighteners. , anti-dripping agents, anti-static agents, anti-fogging agents, anti-blocking agents, fluidity improvers, plasticizers, dispersants, antibacterial agents and the like. These components may be used alone or in combination of two or more.
In the polyamide resin composition of the present invention, the content of the resin component, the glass fiber, the light-transmitting dye, and other additives blended as necessary, etc., so that the total of each component is 100% by mass. is adjusted.

As an embodiment of the polyamide resin composition of the present invention, in particular, as a polyamide resin, 70 mol% or more of the dicarboxylic acid-derived structural units are derived from an α, ω-straight chain aliphatic dicarboxylic acid having 9 to 20 carbon atoms. using a polyamide resin (more preferably, a polyamide resin in which 70 mol% or more of diamine-derived structural units are derived from metaxylylenediamine), and at least one of pyrazolone, perinone and anthraquinone as a light-transmitting dye A form including By adopting such a form, it is possible to more effectively suppress color transfer of the resulting molded article after a wet heat test, and to maintain high mechanical strength.

<Characteristics of resin composition>
The polyamide resin composition of the present invention preferably has a transmittance of 65% or more, more preferably 66% or more, or 67% or more at a wavelength of 1070 nm when molded to a thickness of 1.0 mm. The upper limit is not particularly defined, but 80% or less, or even 75% or less sufficiently satisfies practical performance.

<Method for producing resin composition>
The method for producing the polyamide resin composition of the present invention is not particularly limited, but a method using a single-screw or twin-screw extruder having equipment for devolatilization from a vent port as a kneader is preferred. The polyamide resin component, the glass fiber, and other additives that are blended as necessary may be supplied to the kneader all at once, or the polyamide resin component and other blending components may be sequentially supplied. The glass fibers are preferably supplied from the middle of the extruder in order to suppress crushing during kneading. Also, two or more components selected from each component may be mixed and kneaded in advance.
In the present invention, the light-transmitting dye is a polyamide resin or the like, prepared in advance as a masterbatch, and then kneaded with other components (polyamide resin, glass fiber, etc.) to obtain the resin composition of the present invention. be able to.

The method for producing a molded article using the polyamide resin composition of the present invention is not particularly limited, and molding methods commonly used for thermoplastic resins, i.e., injection molding, blow molding, extrusion molding, press molding, etc. method can be applied. In this case, a particularly preferable molding method is injection molding because of its good fluidity. In injection molding, it is preferable to control the resin temperature to 250 to 300°C.

<Kit>
The polyamide resin composition of the present invention and the light-absorbing resin composition containing a thermoplastic resin and a light-absorbing dye are preferably used as a kit for producing molded articles by laser welding.
That is, the polyamide resin composition of the present invention contained in the kit serves as a light-transmitting resin composition, and a molded product obtained by molding such a light-transmitting resin composition can be obtained by laser beam welding during laser welding. It becomes a transparent resin member for On the other hand, a molded product obtained by molding a light-absorbing resin composition serves as a resin member that absorbs laser light during laser welding.

<<Light absorbing resin composition>>
The light-absorbing resin composition used in the present invention contains a thermoplastic resin and a light-absorbing dye.
Examples of thermoplastic resins include polyamide resins, olefin resins, vinyl resins, styrene resins, acrylic resins, polyphenylene ether resins, polyester resins, polycarbonate resins, polyacetal resins, etc., and have good compatibility with resin compositions. From these points, polyamide resins, polyester resins and polycarbonate resins are particularly preferred, and polyamide resins are more preferred. Moreover, one kind of thermoplastic resin may be used, or two or more kinds thereof may be used.
As the polyamide resin used in the light-absorbing resin composition, the type thereof is not specified, but the above-described xylylenediamine-based polyamide resin is preferable.
Examples of the inorganic filler include fillers capable of absorbing laser light, such as glass fiber, carbon fiber, silica, alumina, talc, carbon black, and inorganic powder coated with a laser-absorbing material, and glass fiber is preferred. The glass fiber has the same meaning as the glass fiber that may be blended in the polyamide resin composition of the present invention, and the preferred range is also the same.
The light-absorbing dye has a maximum absorption wavelength in the wavelength range of the irradiated laser light, that is, in the wavelength range of 800 nm to 1100 nm in the present invention. , thermal black, furnace black, channel black, ketjen black, etc.), red pigments such as iron oxide red, orange pigments such as molybdate orange, white pigments such as titanium oxide), organic pigments (yellow pigments, orange pigments, red pigments, blue pigments, green pigments, etc.). Among them, inorganic pigments are generally preferred because of their high hiding power, and black pigments are more preferred. These light-absorbing dyes may be used in combination of two or more. The content of the light-absorbing dye is preferably 0.01 to 30 parts by mass with respect to 100 parts by mass of the resin component.

In the kit, 80% by mass or more of the components excluding the light-transmitting dye in the polyamide resin composition and the components excluding the light-absorbing dye in the light-absorbing resin composition are common, preferably 90% by mass or more. are more preferably common, and more preferably 95 to 100% by mass are common.

<<Laser Welding Method>>
Next, a laser welding method will be described. In the present invention, a molded article (transmissive resin member) formed from the polyamide resin composition of the present invention and a molded article (absorbent resin member) formed by molding the light-absorbing resin composition are laser-welded and molded. products can be manufactured. By laser welding, the transmitting resin member and the absorbing resin member can be strongly welded together without using an adhesive.
The shape of the member is not particularly limited, but since the members are used by being joined together by laser welding, the shape usually has at least a surface contact portion (flat surface, curved surface). In laser welding, the laser beam transmitted through the transmissive resin member is absorbed by the absorbing resin member and melted, thereby welding the two members together. A molded article formed from the polyamide resin composition of the present invention has high transparency to laser light, and therefore can be preferably used as a transparent resin member. Here, the thickness of the member through which the laser beam is transmitted (thickness in the laser transmission direction at the portion through which the laser beam is transmitted) can be appropriately determined in consideration of the application, the composition of the resin composition, etc., but for example, 5 mm or less. and preferably 4 mm or less.

The laser light source used for laser welding can be determined according to the light absorption wavelength of the light-absorbing dye, and preferably has a wavelength of 800 to 1100 nm. For example, a semiconductor laser or a fiber laser can be used.
In particular, in the kit of the present invention, the resin composition of the present invention and the light-absorbing resin composition are each molded into a test piece of ASTM Standard No. 4 with a thickness of 1.5 mm, and a galvanometer mirror scan type In fiber laser welding, a tensile strength of 1400 N or more can be obtained at a press pressure of 600 N, a laser beam diameter of 2 mm, a laser welding width of 16 mm, and a total energy input for welding of 160 J. As for the upper limit of the tensile strength, even if it is 2000 N or less, it is sufficiently practical. In addition, since the present invention has high transparency, the total amount of energy input during laser welding can be reduced.
In the present invention, the total energy input amount for laser irradiation can be 200 J or less, 180 J or less, or 160 J or less. Even if the total energy input amount is reduced in this way, the value is high in that high laser weldability can be achieved. The lower limit of the total energy input amount can be, for example, 5 J or more, further 10 J or more, particularly 50 J or more.

More specifically, for example, when the transmissive resin member and the absorbent resin member are welded together, first, the portions to be welded of the two are brought into contact with each other. At this time, it is desirable that the two welded portions are in surface contact, and may be flat surfaces, curved surfaces, or a combination of flat surfaces and curved surfaces. Next, a laser beam is irradiated from the transmissive resin member side. At this time, if necessary, a lens may be used to converge the laser light on the interface between the two. The condensed beam is transmitted through the transmissive resin member, is absorbed near the surface of the absorbing resin member, heats up, and melts. Next, the heat is transferred to the transmissive resin member by thermal conduction and melts, forming a molten pool at the interface between the two, and after cooling, the two are joined.
A molded article in which the transmissive resin member and the absorbent resin member are welded in this way has a high welding strength. The term "molded product" as used in the present invention is intended to include not only finished products and parts, but also members forming part of these.

The molded article obtained by laser welding according to the present invention has good mechanical strength, high welding strength, and little damage to the resin due to laser irradiation. It can be applied to electronic equipment parts, office automation (OA) equipment parts, household appliance parts, machine mechanism parts, vehicle mechanism parts, and the like. In particular, food containers, chemical containers, oil product containers, vehicle hollow parts (various tanks, intake manifold parts, camera housings, etc.), vehicle electrical components (various control units, ignition coil parts, etc.), motor parts, It can be suitably used for various sensor parts, connector parts, switch parts, breaker parts, relay parts, coil parts, transformer parts, lamp parts and the like. In particular, the polyamide resin composition and kit of the present invention are suitable for vehicle-mounted camera modules.

EXAMPLES The present invention will be described more specifically with reference to examples below. The materials, usage amounts, ratios, processing details, processing procedures, etc. shown in the following examples can be changed as appropriate without departing from the gist of the present invention. Accordingly, the scope of the present invention is not limited to the specific examples shown below.

Raw material polyamide resin 1:MP10, M/P ratio = 6:4, synthesized according to the following synthesis example.
Polyamide resin 2: MP10, M/P ratio = 7:3, synthesized according to the following synthesis example.
Polyamide resin 3: PXD10, a polyamide resin composed of paraxylylenediamine and sebacic acid was synthesized according to the description in Example 2 of JP-A-2010-070637.
Glass fiber 1: T-756H, urethane-based sizing agent, manufactured by Nippon Electric Glass Co., Ltd., E-glass Glass fiber 2: 301HP, acid-based sizing agent, manufactured by CPIC, E-glass Talc 1: manufactured by Hayashi Kasei, Micron White 5000S
Stabilizer 1: Cuprous iodide, Nihon Kagaku Sangyo Stabilizer 2: 201FF STABILIZER, Nagase Sangyo Release Agent 1: WAX-T1 (EP2036-18), Kao Release Agent 2: Lightamide WH255, Kyoeisha Chemical Co., Ltd. Light-transmitting dye 1: Orient Chemical Industry Co., Ltd., e-BIND LTW-8701H, polyamide 66 and light-transmitting dye masterbatch Light-absorbing dye 1: MA600B, carbon black, Mitsubishi Chemical Co., Ltd.

<Synthesis example of MP10 (M/P ratio = 6:4)>
After heating and dissolving sebacic acid in a reaction vessel under a nitrogen atmosphere, while stirring the contents, the molar ratio of para-xylylenediamine (manufactured by Mitsubishi Gas Chemical Company) and meta-xylylenediamine (manufactured by Mitsubishi Gas Chemical Company) is A 4:6 mixed diamine was slowly added dropwise under pressure (0.35 MPa) so that the molar ratio of diamine to sebacic acid was about 1:1 while the temperature was raised to 235°C. After completion of the dropwise addition, the reaction was continued for 60 minutes to adjust the amount of components having a molecular weight of 1,000 or less. After completion of the reaction, the content was taken out in strand form and pelletized by a pelletizer to obtain a polyamide resin (MP10, M/P=6:4).

<Synthesis example of MP10 (M/P ratio = 7:3)>
After heating and dissolving sebacic acid in a reaction vessel under a nitrogen atmosphere, while stirring the contents, the molar ratio of para-xylylenediamine (manufactured by Mitsubishi Gas Chemical Company) and meta-xylylenediamine (manufactured by Mitsubishi Gas Chemical Company) is A 3:7 mixed diamine was slowly added dropwise under pressure (0.35 MPa) so that the molar ratio of diamine to sebacic acid was about 1:1 while the temperature was raised to 235°C. After completion of the dropwise addition, the reaction was continued for 60 minutes to adjust the amount of components having a molecular weight of 1,000 or less. After completion of the reaction, the content was taken out in strand form and pelletized by a pelletizer to obtain a polyamide resin (MP10, M/P=7:3).

<Gas analysis>
About 50 mg of the sizing agent-attached glass fiber was heated at 280° C. for 1 hour, and the resulting gas was analyzed. Gas analysis was performed by TD-GC/MS (Thermal Desorption (Auto Sampler)-Gas Chromatography/Mass Spectrometry) analysis. The amount of isophorone diisocyanate in the obtained gas was measured by decane conversion. The results are shown in Table 1 below. The unit of isophorone diisocyanate and the total amount of gas is the mass (μg/g) per 1 g of glass fiber.
Gas analysis was performed using TD-20 (TD), GC-2010 Plus (GC), and GCMS-QP2010 Ultra (MS) manufactured by Shimadzu Corporation.

Example, Comparative Example <Compound>
Pellets for forming a light-transmitting member (resin composition) and pellets for forming a light-absorbing member (light-absorbing resin composition) shown in Table 2 or Table 3 below were produced.
Specifically, each component shown in Table 2 or Table 3 below, which will be described later, was weighed at a ratio (unit: % by mass) shown in Table 2 or Table 3 for components other than glass fiber, and dried. After blending, the mixture was fed into a twin-screw extruder (Toshiba Kikai Co., Ltd., TEM26SS) using a twin-screw cassette weighing feeder (Kubota Co., Ltd., CE-W-1-MP) from the root of the screw. In addition, the glass fiber is fed into the above-mentioned twin-screw extruder from the side of the extruder using a vibrating cassette weighing feeder (CE-V-1B-MP, manufactured by Kubota Corporation), and melted and kneaded with the resin component. , pellets for forming a light-transmitting member (resin composition) and pellets for forming a light-absorbing member (light-absorbing resin composition) were obtained.
After drying the pellets for forming the light-transmitting member and the pellets for forming the light-absorbing member obtained above at 120° C. for 4 hours, using an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd., SE-50D), A test piece for a light-transmitting member (1.5 mm thick) and a test piece for a light-absorbing member (1.5 mm thick) were prepared.
In addition, a three-step plate of 90 x 50 mm (30 x 50 mm area for each of 1.0 mm thickness, 2.0 mm thickness, and 3.0 mm thickness) was molded for light transmittance (unit: %) measurement at a wavelength of 1070 nm. , and the light transmittance of a 1.0 mm thick portion was measured.
Molding was carried out at the cylinder temperature and mold surface temperature shown in the table.

<Light transmittance>
The light transmittance (unit: %) at a wavelength of 1070 nm was measured according to ISO13468-1 and ISO13468-2 for the test pieces for light-transmitting members obtained above.

<Welding strength of ASTM No. 4 dumbbell (N)>
Galvano laser welding strength was measured using the test piece for the light-transmitting member and the test piece for the light-absorbing member obtained above.
Specifically, as shown in FIG. 1, the test pieces for the light-transmitting member and the test pieces for the light-absorbing member were overlapped and welded in the combinations shown in Table 4. In FIG. 1, 1 indicates the test piece for the transmitting resin member, 2 indicates the test piece for the absorbing resin member, and 3 indicates the laser irradiation portion. Further, in FIG. 1, the projecting portion at the upper left end of the transmissive resin member 1 and the projecting portion at the lower right end of the absorbing resin member 2 respectively indicate the gate side.
Laser irradiation uses a general galvanometer mirror type scan (sold by Fine Device Co., Ltd., laser beam diameter 2 mm), laser output 30 W to 200 W, scan speed 70 to 2000 mm / sec, scan width (welding width, figure A fiber laser (wavelength: 1070 nm) was irradiated so that the width of 1 and 3) was 16 mm. The total amount of energy input during welding was 160 J, and the pressing pressure for the light-transmitting member test piece and the light-absorbing member test piece was 0.5 MPa (600 N).
Using the welded test piece, the laser welding strength was measured. The welding strength was measured using a tensile tester ("5544 type" manufactured by Instron) (load cell ±2 kN), and the welded and integrated test piece for the light-transmitting member and the test piece for the light-absorbing member were Both ends in the long axis direction were clamped, and the test was performed at a tensile speed of 5 mm/min for measurement. It was evaluated as follows.
A: Tensile strength of 1400 N or more B: Tensile strength of less than 1400 N

As is clear from the above results, the polyamide resin composition of the present invention was excellent in light transmittance.
Furthermore, the kit of the present invention was excellent in laser weldability.

1 Test piece for transmissive resin member 2 Test piece for absorbing resin member 3 Laser irradiation site

Claims (9)

Consists of diamine-derived structural units and dicarboxylic acid-derived structural units, more than 60 mol% of the diamine-derived structural units are derived from metaxylylenediamine, and 70 mol% or more of the dicarboxylic acid-derived structural units have 4 carbon atoms. containing 40 to 80% by mass of a polyamide resin derived from ~20 α,ω-linear aliphatic dicarboxylic acids,
Further, the glass fiber containing a light-transmitting dye and a sizing agent is included, and the proportion of isophorone diisocyanate in the gas component obtained by heating the sizing agent at 280 ° C. for 1 hour is 1 to 20% by mass,
In addition, it contains a stabilizer,
The sizing agent contains a urethane-based sizing agent, and the glass fibers are E-glass fibers,
The stabilizer contains at least one selected from copper compounds, alkali halides, hindered heat stabilizers, and fatty acid metal salts,
Polyamide resin composition. 2. The polyamide resin composition according to claim 1, wherein said stabilizer comprises a copper compound and/or an alkali halide. 3. The polyamide resin composition according to claim 1 or 2, wherein the blending amount of the glass fiber is 25% by mass or more of the polyamide resin composition. 4. The polyamide resin composition according to any one of claims 1 to 3, wherein 70 mol% or more of the constituent units derived from dicarboxylic acid are derived from sebacic acid. A molded article formed from the polyamide resin composition according to any one of claims 1 to 4. A kit comprising the polyamide resin composition according to any one of claims 1 to 4 and a light-absorbing resin composition containing a thermoplastic resin and a light-absorbing dye. The polyamide resin composition and the light-absorbing resin composition are respectively molded into ASTM standard No. 4 pieces with a thickness of 1.5 mm, and subjected to galvanomirror scanning fiber laser welding at a press pressure of 600 N. 7. The kit according to claim 6, wherein the tensile strength is 1400 N or more at a laser beam diameter of 2 mm, a laser welding width of 16 mm, and a total energy input of 160 J during welding. A molded article obtained by molding the polyamide resin composition according to any one of claims 1 to 4, and a molded article obtained by molding a light-absorbing resin composition containing a thermoplastic resin and a light-absorbing dye. A method of manufacturing a molded article, comprising laser welding a. A molded article obtained by molding the polyamide resin composition according to any one of claims 1 to 4 or the kit according to claim 6 or 7.

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